BRPI0617041B1 - PROCESS TO PREPARE A DIFFICTIONAL POLYMER IN a,? " - Google Patents

Abstract

process for the polymerization of one or more addition polymerizable monomers, composition of olefinic copolymer, polymer mixture, and process for preparing a difunctional polymer in <244>, <syn> process for polymerization of one or more addition polymerizable monomers and resulting polymeric composition, said process comprising contacting a polymerizable monomer by adding or mixing monomers in a reactor or reactor zone with a composition comprising at least one polymerization catalyst and one co-catalyst under polymerization conditions, characterized in that at least a portion of said polymerization is performed in the presence of a multicenter exchange agent, thereby causing the composition to have a bimodal molecular weight distribution.

Description

(54) Title: PROCESS TO PREPARE A DIFFUNCTIONAL POLYMER IN A,?

(51) lnt.CI .: C08F 297/08; C08F 2/38 (30) Unionist Priority: 15/09/2006 US 60 / 717,543 (73) Holder (s): DOW GLOBAL TECHNOLOGIES INC.

(72) Inventor (s): EDMUND M. CARNAHAN; PHILLIP D. HUSTAD; BRIAN A. JAZDZEWSKI; ROGER L. KUHLMAN; TIMOTHY T. WENZEL

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PROCESS FOR PREPARING A DIFFUNCTIONAL POLYMER IN a, ω Background of the invention [0001] The present invention relates to a process for polymerizing a monomer or mixture of two or more monomers, for example, mixtures of ethylene and one or more comonomers, for forming a product interpolymer having unique physical properties, a process for preparing such interpolymers, and the resulting polymeric products. In another aspect, the invention relates to articles prepared from these polymers. The inventive polymeric products include mixtures of uniformly germinating chemical composition and relatively wide molecular weight distribution, including a mixture of two or more polymers of uniform monomeric composition, but differing in that at least one component has substantially greater molecular weight comprising regions or segments (blocks) of composition by different chemical characteristics, distinguished from previous weight distribution. In addition, at least one of the constituents of the polymeric mixture contains a linker group which is the rest of a multi-center exchange agent, causing the polymer to have unique physical properties. These polymeric products and mixtures comprising them are usefully used in the preparation of solid articles such as moldings, films, sheets, and foam objects by molding, extrusion, or other processes, and are useful as a component or ingredients in adhesives, laminates, mixtures polymeric, and other end uses. The resulting products are used in the manufacture of automotive components, such as profiles, bumpers and cut-out parts; packaging materials; wire insulation and

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2/130 electrical cables, and other applications.

[0002] The use of certain metallic alkyl compounds and other compounds, such as hydrogen, as chain transfer agents to halt chain growth in olefinic polymerizations is well known in the art. In addition, it is known to use such compounds, especially alkyl aluminum compounds, as cleaners or as co-catalysts in olefinic polymerizations. In Macromolecules, 33, 9192-9199 (2000) the use of certain trialkyl aluminum compounds as chain transfer agents in combination with certain paired zirconocene catalyst compositions resulted in polypropylene mixtures containing small amounts of polymeric fractions containing both segments of chain isotactic as well as atactic. In Liu and Ritter, Macromolecular Rapid Comm., 22, 952-956 (2001) and in Bruaseth and Rytter, Macromolecules, 36, 3026-3034 (2003) polymerized mixtures of ethylene and 1-hexene by a similar catalyst composition containing agent of aluminum trimethyl chain transfer. In the last reference, the authors summarized the prior art studies as follows (some citations were omitted):

[0003] A mixture of two metallocenes with known polymerization behavior can be used to control polymer microstructure. Several ethylene polymerization studies have been carried out by mixing two metallocenes. The common observations were that, combining catalysts that separately give polyethylene with different Mw, polyethylene with wider MWD and in some cases with bimodal MWD can be obtained. Soares and Kim (J. Polym. Sci., Part A: Polym. Chem.,

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3/130 ethylene / l-hexene of the mixtures and Et (Ind) ₂ ZrCl ₂ / CGC (catalyst supported by silica. Heiland

38, 1408-1432 (2000)) developed a criterion to test the MWD bimodality of polymers prepared by double single-site catalysts, as exemplified by de and

copolymerization of Et (Ind) ₂ ZrCl ₂ / Cp ₂ HfCl ₂ constricted geometry)

Kaminski (Makromol. Chem., 193, 601-610 (1992)) studied a mixture of Et (Ind) ₂ ZrCl ₂ and the hafnium analog in copolymerization of ethylene and 1-butene.

[0004] These studies do not contain any interaction between the two different sites, for example, by re-adsorption of a chain terminated at the alternative site. However, such reports have been published for propylene polymerization. Chien et al. (J. Polym. Sci., Part A: Polym. Chem., 37, 2439-2445 (1999), Makromol., 30, 3447-3458 (1997)) studied the polymerization of propene by homogeneous binary zirconocene catalysts. A mixture of isotactic polypropylene (i-PP), atactic polypropylene (a-PP), and a stereo block fraction with a binary system comprising an isospecific precursor and a non-specific precursor with a borate and TIBA as a co-catalyst were obtained . Using a binary mixture of isospecific and zionconospecific zirconocenes, a mixture of isotactic polypropylene (i-PP), syndiotatic polypropylene (s-PP), and a stereoblock fraction (PP-b-s-PP) was obtained. The mechanism for the formation of the stereoblock fraction has been proposed to involve the exchange of propagating chains between the two different catalytic sites. Przybyla and Fink (Acta Polym., 50, 77-83 (1999)) used two different types of metallocenes (isospecific and syndiospecific) supported on the same silica for

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4/130 propylene polymerization. They reported that, with a certain type of silica support, chain transfer occurred between the active species in the catalyst system, and PP stereoblocks were obtained. Lieber and Brintzinger (Macromol. 3, 9192-9199 (2000)) proposed a more detailed explanation of how the transfer of a growing polymer from one type of metallocene to another occurs. They studied the polymerization of propene by catalyst mixtures of two different loop-zirconocenes. First, the different catalysts were studied individually with respect to their tendency to exchange alkylpolymeryl with the alkyl aluminum activator and then paired with respect to their ability to produce polymers with a stereoblock structure. They reported that the formation of stereoblock polymers by a mixture of zirconocene catalysts with different stereoselectivities depends on the efficient polymer exchange between the Zr catalyst centers and the Al co-catalyst centers.

[0005] Brusath and Rytter then released their own observations using paired zirconocene catalysts to polymerize ethylene / l-hexene mixtures and reported the effects of the influence of the double site catalyst on polymerization activity, comonomer incorporation, and polymer microstructure using methyl alumoxane co-catalyst.

[0006] Analysis of the previous results indicated that Rytter and collaborators probably failed to use combinations of catalyst, co-catalyst and a third component that were able to re-adsorb the polymeric chain of the chain transfer agent on both

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5/130 the active catalytic sites, that is, they failed to obtain re-adsorption in both directions. Although indicating that the end of the chain due to the presence of trimethyl aluminum probably occurred with respect to the polymer formed from the catalyst incorporating minimally comonomer, and from then on, there was probably an exchange of polymer with a more open catalytic site followed by continuous polymerization, it seems to be lacking evidence of the reverse flow of polymeric binders in the reference. In fact, in a later communication, Rytter et al., Polymer, 45, 7853-7861 (2004), reported that there was really no chain transfer between the catalytic sites in the previous experiments. Similar polymerizations have been reported in WO 98/34970.

[0007] Nas patents U.S n ² s 6,380,341 and 6,169,151, reported that í the use in a catalyst in metallocene fluxionary, this is one capable metallocene in conversion

relatively simple between two stereoisomeric forms having different polymerization characteristics, such as, different reactivity ratios result in the production of olefinic copolymers having a blocky structure. Unfavorably, the respective stereoisomers of such metallocenes generally fail to have a significant difference in polymer forming properties and are unable to form both amorphous and very crystalline block copolymer segments, for example, from a given monomeric mixture under fixed reaction conditions . In addition, since the relative ratio of the two catalyst fluxionary forms cannot vary, there is no ability, using fluxionary catalysts, to vary the composition

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6/130 of polymeric block or to vary the ratio of the respective blocks.

[0008] In JACS, 2004, 126, 10701-10712, Gibson et al., Discuss the effects of catalyzed live polymerization on molecular weight distribution. The authors define catalyzed live polymerization in this way: ... if the transfer of chain to aluminum is the only transfer mechanism and the exchange of the growing polymer chain between the transition metal and the aluminum centers is very fast and reversible, polymer chains will appear to be growing in aluminum centers. This can then reasonably be rewritten as a catalyzed chain growth reaction in aluminum. An attractive manifestation of this type of chain growth reaction is a Poisson distribution of the molecular weights of products, as opposed to the Schulz-Flory distribution that originates when β-transferência transfer accompanies propagation.

[0009] The authors reported the results gives live homopolymerization catalyzed from ethylene using one iron-containing catalyst in combination with ZnEt2, ZnMe2, or

Zn (i-Pr) 2 · Homoleptic alkyls of aluminum, boron, tin, lithium, magnesium and lead did not induce catalyzed chain growth. The use of GaMe3 as a co-catalyst resulted in the production of a polymer having narrow molecular weight distribution. However, after analyzing time-dependent product distribution, the authors concluded that this reaction was not a simple catalyzed chain growth reaction. Similar processes employing similar catalysts have been described in US Patent No 5,210,338 ^2s, 5,276,220, and 6,444,867.

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7/130 [0010] It is known in the art that the presence of long chain branching (LCB) can improve certain polymeric characteristics, especially processability and resistance to melting. The presence of LCB in a polymer is characterized by the occurrence of polymeric portions of a length greater than that of any remaining C3-8 olefinic comonomer attached to the main polymeric chain. In the prior art techniques, long chain branching can be generated in a polymer by incorporating a vinyl-terminated macro-monomer (or deliberately added or formed at the site during polymerization such as by eliminating β-hydride) or by action of the polymerization catalyst itself or by the use of a binding agent. Generally, these methods suffer from incomplete incorporation of the vinyl-terminated macromonomer or binder portion into the polymer, and / or from a lack of control over the extent of LCB for given process conditions.

[0011] There remains a need in the art for a polymerization process that is capable of preparing copolymers having unique properties in a high yield process adapted for commercial use. In addition, it would be desirable to provide an improved process for preparing polymers, including copolymers of two or more comonomers such as ethylene and one or more comonomers, by using a multicentre exchange agent (MSA) to introduce coupling and branching properties, including branching long-chain, in the resulting pseudo-block copolymers, in a controlled manner. More specifically, it would be desirable to provide a method for generating long chain branching in olefinic polymers that does not require

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8/130 incorporation of a polymerizable functional group, such as a vinyl group in the polymer chain. Furthermore, it would be desirable to provide such an improved method for, in a continuous process, preparing copolymer products in branched or coupled pseudoblocks.

Summary of the invention [0012] According to the present invention there is now provided an olefinic polymer composition characterized exclusively by a spatially wide multimodal molecular weight distribution and a process for preparing it. In particular, the present composition comprises two or more olefinic polymers differing in molecular weights, the weight average molecular weights of at least two such polymers differing by approximately an integer multiple. The polymeric mixture is prepared at the site by the polymerization of one or more polymerisable monomers by addition, preferably two or more polymerisable monomers by addition, especially ethylene and at least one copolymerizable comonomer, propylene and at least one different copolymerizable comonomer having 4 or more carbon atoms, optionally comprising blocks or multiple segments of differentiated polymeric properties and composition, especially blocks or segments comprising different levels of comonomer incorporation. The process comprises contacting a polymerizable monomer by adding or mixing monomers under addition polymerization conditions and a multi-center exchange agent.

[0013] As the polymer is comprised of at least a little bit of polymer joined together by means of one or more remains of a

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9/130 multicentre exchange agent, the resulting polymeric composition has unique physical and chemical properties when compared to random mixtures of polymers of the same crude chemical composition and when compared to copolymers in pseudoblocks with a lack of exchange agent in multiple exchange centers. Depending on the number of active centers in the multi-center exchange agent, that is, if each exchange agent molecule has two, three or more active exchange sites, and the number of separate additions of such an agent, the resulting polymer may be distinctly multimodal or form a more uniform broad distribution of molecular weights of polymers and / or branched or multiply branched. In general, the resulting polymers contain a reduced incidence of cross-linked polymer formation as evidenced by a reduced gel fraction. Preferably, the polymers of the invention comprise less than 2 percent crosslinked gel fraction, more preferably less than 1 percent crosslinked gel fraction, and most preferably less than 0.5 percent crosslinked gel fraction.

[0014] In another embodiment of the invention a copolymer is provided, especially a copolymer comprising ethylene in polymerized form and a copolymerizable comonomer, propylene and at least one copolymerizable comonomer having from 4 to 20 carbon atoms, or 4-methyl-1-pentene and at least one different copolymerizable comonomer having from 4 to 20 carbon atoms, said copolymer comprising two or more, preferably two or three intramolecular regions comprising different chemical or physical properties, especially regions of comonomer incorporation

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10/130 differentiated, joined in a dimeric, linear, branched or poly-branched polymeric structure. Such polymers can be prepared by changing the polymerization conditions during a polymerization that includes a multi-center exchange agent, for example, using two reactors with different comonomer ratios, multiple catalysts with different comonomer incorporation capabilities, or a combination of such process conditions , and optionally a polyfunctional coupling agent.

[0015] In another embodiment of the invention there is provided a process and the resulting polymer, said process comprising: polymerizing one or more olefinic monomers in the presence of an olefinic polymerization catalyst and a multi-center exchange agent (MSA) in a zone or polymerization reactor thus causing the formation of at least some amount of a polymer joined with the rest of the multicentre exchange agent.

[0016] In yet another embodiment of the invention, a process is provided and the resulting polymer, said process comprising: polymerizing one or more olefinic monomers in the presence of an olefinic polymerization catalyst and a multi-center exchange agent (MSA) in a zone or polymerization reactor thus causing the formation of at least some amount of a polymer joined with the remainder of the multicentre exchange agent within the zone or reactor; discharge the reaction product from the first reactor or zone to a second reactor or zone operating under polymerization conditions that are distinguishable from those of the first reactor or zone; transfer at least some of the starting polymer bonded with the rest of the multi-center exchange agent

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11/130 to an active catalyst site in the second reactor or polymerization zone by means of at least one remaining exchange site of the multi-center exchange agent; and carrying out polymerization in the second reactor or polymerization zone in order to form a second polymeric segment connected to a part or all of the initial polymer by means of a remainder of the multicentre exchange agent, said second polymeric segment having polymeric properties distinguishable from the polymeric segment initial.

[0017] Most desirably, the polymeric products here comprise at least some amount of a polymer containing two or more blocks or segments joined by means of a rest of the multicentre exchange agent. The product generally comprises a first polymer having a first molecular weight and at least some amount of a second polymer having a molecular weight that is approximately an integer multiple of the molecular weight of the first polymer, the whole number being equal to the number of centers of exchange in the exchange agent. The polymer recovered from the present process can be terminated to form polymers of conventional type, coupled through the use of polyfunctional coupling agent to form copolymers in multiblocks, including dendrimeric or hyper-branched copolymers, or functionalized by converting residues of the multicentre exchange agents into vinyl , hydroxyl, amine, silane, carboxylic acid, carboxylic acid ester, ionomer, or other functional groups, according to known techniques.

[0018] In an embodiment of the invention a two-center exchange agent is used, resulting in polymers containing

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12/130 at least some amount of a polymer containing the remainder of the two-center exchange agent and an additional polymer growth step based thereon. The resulting product is a polydispersed polymer mixture prepared at the site, typically having a bimodal molecular weight distribution with a peak approximately twice the molecular weight of the other. If both a multi-center exchange agent and a single-center exchange agent are employed, or simultaneously or sequentially in the same polymerization, the result is a mixture of polymeric products having polydispersed molecular weight distribution and multi-block copolymer properties.

[0019] In yet another embodiment of the invention, the multi-center exchange agent used in the previous processes is a two-center exchange agent, which exclusively causes the formation of a product comprising distinct polymeric segments after undergoing sequential polymerization in two reactors or linked zones in series. In an additional preferred embodiment, the active sites of the two-center exchange agent are located close to or at both end points of a linear exchange agent (or form an exchange agent such by ring opening a cyclic MSA) and result in formation of terminally functionalized polymers, including those polymers converted to additional functional groups as previously disclosed. Hereinafter, the exchange agents of two previous centers will be referred to as exchange agents of two centers α, ω due to their usefulness in the formation of difunctionalized polymers in a, ω, particularly polyvinyls substituted by di-vinyl in a, ω or by provision 870170056094, of 08/04/2017, p. 19/141

13/130 hydroxy in α, ω having molecular weights from 500 to 10,000, preferably from 1000 to 6000. Such products can be prepared by the reaction of oxygen or an electrophile containing oxygen with a polymer dimetalized in alpha / Omega formed by incorporating the present agent exchange of two centers at α, ω, or by displacing the metal center with an olefin, such as ethylene, to produce oa, (0diene, which can then be converted to diol by hydroformylation and hydrogenation if desired. Such polymers, especially versions their low molecular weight are useful for conversion to polyurethanes, polyesters, and other products used in the production of coatings, adhesives, sealants and elastomers.

[0020] In previous embodiments of the invention, the resulting polymer can be linear or contain one or more branching centers depending on whether an exchange agent is used or two, three or more centers. Most desirably, the foregoing copolymers are characterized by terminal blocks or segments of polymer having greater tactility or crystallinity than at least some remaining blocks or segments. Even more preferably, the polymer is a three-block copolymer comprising a central polymeric block or segment that is relatively amorphous or even elastomeric.

[0021] In another embodiment, MSA is a three-center exchange agent and the resulting polymers are characterized by the presence of long chain branching. In this embodiment, moreover, a method is provided for generating long chain branching in olefinic polymers without the use of a polymerizable functional group, such as a group

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14/130 vinyl. Instead, the LCB branch point is the remainder of a three-center MSA. Since the extent of LCB in the polymer is easily controlled by adding the three-center MSA for a polymerization reaction at the desired rate, the resulting process is advantageous over prior art processes.

[0022] Still in a further embodiment of the present invention, a polymeric mixture is provided comprising: (1) an organic or inorganic polymer, preferably an ethylene or propylene homopolymer and / or an ethylene or propylene copolymer with one or more comonomers copolymerisables, and (2) a polymer or polymeric mixture according to the present invention or prepared according to the process of the present invention.

Brief description of the drawings [0023] Figure 1 is a schematic representation of a process for forming a polymeric composition according to the present invention using a single catalyst.

[0024] Figure 2 is a schematic representation of an alternative process for forming a polymeric composition according to the present invention using a single catalyst. [0025] Figure 3 is a schematic representation of a process for forming a multimodal polymer composition according to the present invention using two different catalysts.

[0026] Figure 4 is a schematic representation of a process for forming a two-block copolymer composition according to the present invention using two different catalysts.

Detailed description of the invention

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15/130 [0027] Here, all references to the Periodic Table of Elements will refer to the Periodic Table of Elements published and registered by CRC Press, Inc., 2003. Likewise, all references to a group or groups will refer to the group or groups reflected in this Periodic Table of the Elements using the IUPAC system to number groups. Unless otherwise stated, implicit in context, or customary in the technique, all parts and percentages are based on weight. For the purposes of United States patent practice, the contents of any patent, patent application, or publication mentioned herein are incorporated in their entirety by reference (or the US version of them is also incorporated by reference) especially with respect the dissemination of synthetic techniques, definitions (to the extent not inconsistent with any definitions provided herein) and general knowledge of the technique.

[0028] The term comprising and derivatives thereof is not intended to exclude the presence of any additional portion, component, step or procedure, whether or not it is disclosed herein. In order to avoid any debt, all compositions claimed herein using the term comprising may include any additive, adjuvant, or additional or polymeric compound or differently, unless otherwise stated. In contrast, the term essentially consists of excluding any other portion, component, step or procedure from the scope of any subsequent mention, except those that are not essential to operability. The term consisting of excludes any portion, component, step or procedure not specifically described or listed. The term or, unless otherwise stated

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16/130 in contrast, refers to members listed individually as well as in any combination.

[0029] The term polymer includes both homopolymers, that is, homogeneous polymers prepared with a single monomer, and copolymers (referred to here to allow exchange or substitution as interpolymers), meaning polymers prepared by reacting at least two monomers or otherwise containing the same blocks or segments chemically differentiated even if formed from a single monomer. More specifically, the term polyethylene includes ethylene homopolymers and ethylene copolymers and one or more C3-8 α-olefins. If used, the term crystalline will refer to a polymer that has a crystalline melting point or first order transition (Tm) determined by differential scanning calorimetry (DSC) or equivalent technique. The term can be used to

to allow exchange or replacement with the term semicrystalline. 0 term amorphous refers to one polymer lacking a fusion point crystalline. 0 term elastomer or

elastomeric refers to a polymer or polymeric segment having Tg less than 0 ° C, more preferably less than -15 ° C, most preferably less than -25 ° C, and a sample of which, when deformed by application of stress, is generally able to recover its size and shape when the deforming force is removed. Specifically, as used herein, elastic or elastomeric means to be that property of any material that, due to the application of an oblique force, allows the material to be possible to stretch to a length that is at least 25 percent greater than its non-inclined length. without rupture, and

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17/130 that will cause the material to recover at least 40 percent of its elongation in response to the release of force. A hypothetical example that would satisfy this definition of an elastomeric material would be a 1 cm sample that can be stretched to a length of at least 1.25 cm and that, after being stretched to 1.25 cm and released, will recover to a length of no more than 1.15 cm. Many elastic materials can be stretched to well over 25 percent of their relaxed length, and many of these will recover substantially to their original relaxed length in response to the release of the elongation force.

[0030] The term pseudobloc copolymer refers to a copolymer comprising two or more blocks or segments of different chemical or physical properties, such as variable comonomer content, crystallinity, density, tactility, region error, or other property. Non-adjacent blocks are not necessarily of identical chemical composition, but can vary in one or more of the previous aspects, in the composition of all other blocks or regions. Compared to random copolymers, pseudo-block copolymers have sufficient differences in chemical properties, especially crystallinity, between blocks or segments, and sufficient block lengths to achieve one or more of the desired properties of true block copolymers, such as thermoplastic / elastomeric properties, while at the same time being sensitive to preparation in conventional olefinic polymerization processes, especially continuous solution polymerization processes employing catalytic amounts of polymerization catalysts. The polymers and blocks of

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18/130 themselves comprise a wider distribution than conventional block copolymers, which in theory have molecular weight distributions of 1.0. Copolymers in pseudoblocks have broader molecular weight distributions. In addition, the respective blocks of a pseudoblock copolymer desirably have a PDI obeying a Schulz-Flory distribution instead of a Poisson distribution.

[0031] That trained technician will quickly understand that in an incorporation of the present inventive process the MSA can be added once, more than once (intermittently) or added continuously to each polymerization zone or reactor employed in the polymerization. Most desirably, MSA is added to the reaction mixture before the polymerization starts, at the same time as the polymerization starts, or at least for a significant portion of the time the polymerization is carried out, especially in the first reactor if several reactors are used. The complete mixing of MSA and reagent mixture can be caused by active or static mixing devices or by the use of any stirring or pumping device employed in mixing or transferring the reagent mixture. [0032] As used herein with respect to a chemical compound, unless specifically stated otherwise, the singular includes all isomeric forms and vice versa (eg hexane, includes all hexane isomers individually or collectively). The terms: compound and complex are used, in order to allow exchange or substitution here referring to organic, inorganic and organometallic compounds. The term atom refers to the

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19/130 minor constituent of an element regardless of ionic state, that is, whether or not it has a partial charge or charge or if it is attached to another atom. The term heteroatom refers to an atom other than carbon or hydrogen. Preferred heteroatoms include: F, Cl, Br, N, Ο, Ρ, B, S, Si, Sb, Al, Sn, As, Se and Ge.

[0033] The term hydrocarbyl refers to monovalent substituents containing only hydrogen and carbon atoms, including cyclic or non-cyclic, saturated or unsaturated, branched or unbranched species. Examples include alkyl, cycloalkyl, alkenyl, alkadienyl, cycloalkenyl, cycloalkadienyl, aryl, and alkynyl groups. Substituted hydrocarbyl refers to a hydrocarbyl group that is substituted with one or more non-hydrocarbyl substituent groups. The terms, containing heteroatom or heterohydrocarbyl 'monovalent groups in which at least one atom other than hydrogen or carbon is present together with one or more carbon atoms and one or more hydrogen atoms term heterocarbyl refers to groups containing one or more carbon atoms and one or more hetero atoms and no hydrogen atoms. The bond between the carbon atom and any heteroatom, as well as the bonds between any two hetero atoms, can be saturated or unsaturated. Thus, an alkyl group substituted with a heterocycloalkyl, substituted hetero-cycloalkyl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, dihydrocarbil boryl, dihydrocarbil phosphine, dihydrocarbil amino, trihydrocarbil silyl, hydrocarbil-thio or hydrocarbil-selene is within the limits of coverage of the term hydrocarbyl refer to

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20/130 heteroalkyl. Examples of suitable heterolakyl groups include cyano, benzoyl, (2-pyridyl) methyl, and trifluoromethyl groups.

[0034] As used here, the term aromatic refers to a conjugated, cyclic, polyatomic ring system containing (4δ + 2) π electrons, where δ is an integer greater than or equal to 1. The fused term, as as used herein, with respect to a ring system containing two or more polyatomic cyclic rings means that with respect to at least two rings of the same, at least one pair of adjacent atoms is included in both rings. The term aryl refers to a monovalent aromatic substituent which can be a single aromatic ring or multiple aromatic rings fused to each other, covalently bonded or linked to a common group such as a methylene or ethylene moiety. Aromatic rings can include phenyl, naphthyl, anthracenyl, and biphenyl, among others.

[0035] Substituted aryl refers to any aryl group in which one or more hydrogen atoms attached to any carbon is replaced by one or more functional groups such as alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, hetero-cycloalkyl, hetero- substituted cycloalkyl, halogen, haloalkyl (e.g. CF3), hydroxy, amino, phosphide, alkoxy, amino, uncle, nitro, and both saturated and unsaturated cyclic hydrocarbons that fuse to aromatic rings, covalently linked or linked to such a common group as a methylene or ethylene portion. The common linking group can also be a carbonyl group as in benzophenone or oxygen as in diphenyl ether or nitrogen as in diphenylamine.

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21/130 [0036] The term comonomer incorporation index refers to the percentage of comonomer incorporated in a copolymer prepared by the considered catalyst. The selection of metallic complexes or catalyst compositions having the maximum difference in comonomer incorporation rates under different polymerization conditions, in an embodiment of the present invention, results in copolymers of two or more monomers having the maximum difference in block or segment properties, as as density, for the same distribution of comonomer composition. Accordingly, the comonomer incorporation index is determined by the use of NMR spectroscopy techniques. This index can also be estimated based on reactivity of monomers and kinetics of reactors according to known theoretical techniques.

[0037] In a polymer containing distinguishable segments each segment can be the same or chemically different or germ characterized by a distribution of properties. The last result can be achieved if the polymer chain experiences different polymerization conditions in different reactors or polymerization zones during formation. The different polymerization conditions in the respective reactors or zones include the use of different monomers, different comonomers, or different monomer / comonomer ratios, different polymerization temperatures, pressures or partial pressures of various monomers, different catalysts, simultaneous use of exchange agents multicentre, different monomer gradients, or any other difference that leads to the formation of a distinguishable polymeric segment. In this way, at least a portion of the polymer resulting from the present process

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22/130 can comprise two, three, or more, preferably two or three types of differentiated polymer segments arranged in an intramolecular manner.

[0038] In accordance with the present invention, by selecting very active catalytic compositions capable of rapid transfer of polymeric segments to and from a multi-center exchange agent, a polymeric product is formed having at least two different molecular weight fractions. Due to the use of at least one multicentre exchange agent and catalysts capable of rapid and efficient exchange of growing polymer chains, the polymer experiences discontinuous polymeric growth and transfer to a remainder of the multicentre exchange agent, thus forming at least some polymer having approximately double, triple or another multiple of the molecular weight of a remaining component of the polymeric mixture, and optionally, chemically distinct polymeric segments. [0039] The term approximately used with respect to the comparison of fashions in a multimodal molecular weight distribution of a polymeric mixture here means that the average molecular weight of the highest molecular weight component of the multimodal mixture is within the limits of 15 percent, preferably within of the 10 percent limits, of an integer multiple of the lowest molecular weight component, said integer being 2 or greater.

Monomers [0040] Monomers suitable for use in the preparation of the copolymers of the present invention include any addition-curable monomers, preferably any olefinic or diolefinic monomer, more preferably any Appetition 870170056094, from 08/04/2017, p. 29/141

23/130 olefin, and most preferably ethylene and at least one copolymerizable comonomer, propylene and at least one copolymerizable comonomer having from 4 to 20 carbon atoms, or 4-methyl-1-pentene and at least one copolymerizable comonomer having from 4 to 20 carbon atoms. Examples of suitable monomers include 2 to 30 standard or branched α-olefins, preferably 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1 -hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1hexadecene, 1-octadecene, and 1-eicosene; cycloolefins from 3 to 30, preferably from 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2norbornene, tetra-cyclododecene, and 2-methyl-1, 4,5,8- dimethane 1,2,3,4,4a, 5,8,8a-octahydro-naphthalene; di and polyolefins, such as butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1, 3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, norbornene ethylidene, norbornene vinyl, di-cyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene- 8-methyl-1,7-nonadiene, and 5,9-dimethyl-1,4,8decatriene; aromatic vinyl compounds such as mono- or polyalkyl styrenes (including styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, o, p-dimethyl styrene, oethyl styrene, m-ethyl styrene and p-ethyl-styrene), and derivatives containing functional group, such as methoxy styrene, ethoxy styrene, vinyl benzoic acid, vinyl benzyl acetate, hydroxy styrene, o-chloro-styrene, p-chloro-styrene, divinyl-benzene, 3- phenyl-propene, 4-phenyl-propene, and α-methyl-styrene, vinyl chloride, 1,2-difluoroethylene,

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1,2-dichlorethylene, tetrafluoroethylene, and 3,3,3-trifluoro-1propene, as long as conditions are used.

monomer is polymerizable in [0041] Preferred monomers or monomer mixtures for use in combination with at least one MSA here include ethylene, propylene, mixtures of ethylene with one or more monomers selected from the group consisting of propylene, 1butene, 1-hexene, 4 -methyl-1-pentene, 1-octene, and styrene; and mixtures of ethylene, propylene and a conjugated or unconjugated diene.

Exchange agents [0042] The term, exchange agent or chain exchange agent, refers to a compound or mixture of compounds that is capable of causing transfer of polymerase between the various catalytic sites active under the conditions of polymerization. That is, the transfer of a polymeric fragment to and from an active catalytic site occurs in a simple manner. In contrast to the exchange agent, a chain transfer agent causes polymeric chain growth to stop and corresponds to a one-time transfer of growing polymer from the catalyst to the transfer agent. Desirably, the chisel intermediate between the chain exchange agent and the polymer polymer chain is sufficiently stable that chain termination is relatively rare.

[0043] The term, multicentre exchange agent refers to a compound or molecule containing more than one, preferably 2 or 3, portions of exchange agent attached to a polyvalent linker group. In practice, the appropriate exchange agent portions preferably include

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25/130 metal centers derived from a metal selected from Groups 2-14 of the Periodic Table of the Elements and having one or more valences available capable of reversibly binding to a growing polymer chain prepared by a polymerization catalyst by coordination. At the same time that the exchange agent portion binds to the growing polymeric chain, the remainder of the remaining polyvalent binding group after the loss of the exchange agent portion or portions incorporates or otherwise binds to one or more catalytic sites active, thus forming a catalytic composition containing an active coordination polymerization site capable of polymeric insertion in at least one terminal of what was originally the polyvalent ligand group. Desirably, at least 0.5 percent, preferably at least 1 percent, more preferably at least 2 percent and most preferably at least 3 percent and up to 99 percent, preferably up to 98 percent, and most preferably up to 95 percent percent of the total polymer comprises a polymer component of higher molecular weight. Particularly desirable compositions are mixtures of two or more polymers prepared according to the invention in which 25, 50 or 75 percent of the total mixture is of the component with the highest molecular weight.

[0044] Despite being linked to the growing polymeric chain, the exchange agent desirably does not change the polymeric structure or incorporates additional monomer. That is, the exchange agent also does not have significant catalytic properties for polymerization. In fact, the exchange agent forms a metal / alkyl interaction or other type of interaction with the polymeric portion until the

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26/130 transfer of the polymeric portion to an active polymerization catalyst site will occur again. Transferring the same exchange agent site back to the original catalyst merely results in an increase in the molecular weight of the polymer. The transfer to a different catalyst (if more than one type of catalyst is employed) results in the formation of a distinguishable type of polymer, due, for example, to a difference in monomer incorporation properties, tactility, or other property of the subsequent catalyst. The transfer through one of the remaining exchange sites results in a growth stage at a different point in the polymeric molecule. With a two-center exchange agent, at least some of the resulting polymer is approximately twice the molecular weight of the remaining polymeric segments. In certain circumstances, the subsequently formed polymer region also has a distinguishable physical or chemical property, such as a different monomer or comonomer identity, a difference in the distribution of the comonomer composition, crystallinity, density, tactility, regio-error, or other property , compared to the polymer formed at other times during polymerization. Subsequent repetitions of the previous process may result in the formation of segments or blocks having a multiplicity of different properties, or a repetition of a previously formed polymer composition, depending on the rates of polymer change, number of reactors or zones within the reactor, transport between reactors or zones, number of different catalysts, monomer gradient in the reactors, and so on. The polymers of the invention can be

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27/130 characterized by a narrow or wide molecular weight distribution. Polymers having a narrow molecular weight distribution typically have a PDI (Mw / Mn) of 2.0 to 2.8. Polymers having a broad PDI are those with a PDI of 2.8 to 20, more preferably 3.0 to 10.

[0045] The process of the invention which employs a two-center chain exchange agent and a single catalyst can be further elucidated by reference to Figure 1, where an activated catalyst, 10, and a multi-center exchange agent, 14, is illustrated. containing two separate chain exchange sites, M. Under polymerization conditions with chain growth the activated catalyst forms a polymer chain, 12. In step 1, the exchange agent exchanges a chain exchange portion with a combination of catalyst / polymer, thus linking the polymeric chain, 12, to a chain exchange portion, M. Simultaneously the rest of the chain exchange agent, 14, resulting from loss of a portion, M, binds to an active catalyst site, forming a new species, 11, capable of continuing polymerization. In step 2, the catalytic site produces a new polymeric segment, 12a, thus forming a polymeric segment joined to the rest of the chain exchange, 14. There is no chain growth in the other species of the reaction, the polymeric chain, 12 terminated with rest chain exchange agent, M. In step 3, chain transfer occurs followed by polymerization thus forming a new polymeric segment, 12b, linked to the original polymeric segment 12, and regeneration of a two-center chain exchange agent MSA including polymeric extension 12a connected to plot 14 and two M plots. In step 4, a final transfer of this

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Two-center chain exchange agent MSA via the second exchange center results in the formation of active catalyst attached to the combined MSA portion, 14 and polymeric segment 12a and separate polymeric segment 12 attached to the polymeric segment 12b. Although represented as separate polymeric regions, it should be understood that the two polymers 12 and 12b formed under approximately identical polymerization conditions by the same catalyst species are substantially identical, and under conditions of homogeneous polymerization, the combination of polymers 12 and 12b is essentially indistinguishable of the polymer itself 12. In step 5, a new polymeric segment 12c is formed at the active catalytic site attached to the rest of MSA 14. The end in step 6 results in the formation of two polymeric products, 18 and 19, which are distinguishable based on weight molecular as well as the presence of the residue of the two-center chain exchange agent, 14, in the polymeric product 18.

[0046] The transfer of the growing polymer can occur several times with continuous growth of the polymeric segment each time it binds to an active catalyst. Under uniform conditions of polymerization, the growing polymer blocks are substantially homogeneous, although their size is in accordance with a size distribution, desirably a very likely distribution. If different polymerization conditions occur such as the presence of different monomers or monomer gradients in a reactor, multiple reactors operating under different process conditions, and so on, the respective polymeric segments can also be distinguished based on differences in physical and chemical properties . The exchange

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29/130 chain and additional growth can continue as before for any number of cycles. However, the resulting product mixture contains at least two separate species distinguishable mainly based on the difference in molecular weight, with the polymeric species 18, containing the remainder of the multi-center exchange agent, 14, having approximately twice the size of the polymeric product, 19. Consequently, in this case a product of substantially homogeneous composition and having a bimodal molecular weight distribution is formed.

[0047] In Figure 2, a similar but less common process is illustrated in which simultaneous growth occurs in both centers of a two-center MSA. In particular, an activated catalyst, 20, and a multi-center exchange agent, 24 containing two separate chain exchange sites, M, are present in a reactor operating under polymerization conditions. The catalyst forms a polymeric segment 22. In step 1, the exchange agent exchanges one of the two active sites with the catalyst / polymer combination, thus forming a species comprising the polymeric chain, 22 linked to M. Simultaneously, the rest of the agent of chain exchange, 24-M binds to an active catalyst site, forming a new species, 21 capable of continuing polymerization. In step 2, the catalyst site produces a new polymeric segment, 22a, thus forming a polymeric segment linked to the rest of the chain exchange, 24. In step 3, growth and transfer of the chain occurs the remaining site of the two center MSA while still attached to the original catalyst, thus forming a polymeric species, 26 having two active catalyst sites separated by

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30/130 polymeric segment 22a and the rest of the exchange agent, 24. In step 4, the continued polymerization of both active sites forms a polymeric species, 27 containing two polymer growth regions, 22a and 22b joined by the rest of the agent exchange of two centers with active catalyst sites at each end. The termination of chain growth in step 5 results in the formation of two polymeric products, 28 and 29, which are distinguishable based on the molecular weight as well as the presence of the two-center chain exchange agent residue, 24, in the polymeric product 28 .

[0048] Figure 3 illustrates the process of the invention employing a two-center chain exchange agent and two different catalysts, C 'and C, where a first activated catalyst, C', forms a polymeric chain, 32. The second activated catalyst, C ', also forms a polymeric segment that is not shown. In step 1, the exchange agent exchanges a chain exchange portion with a catalyst / polymer combination, thereby linking the polymer chain, 32, to a chain exchange portion, M. Simultaneously, the rest of the exchange agent chain, 34 resulting from the loss of a portion, M, binds to an active catalyst site, forming a new species, 31 capable of continuing polymerization. In step 2, the catalyst site produces a new polymeric segment, 32a, thus forming a polymeric segment linked to the rest of the chain exchange, 34. No chain growth occurs in the polymeric chain terminated by the exchange agent, 32. In step 3, transfer occurs involving the second catalyst, C, followed by polymerization to form a polymeric species, 35,

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31/130 comprising the polymeric segment, 36 connected to the polymeric chain 32 originally formed. The polymeric segment, 36, has polymeric properties, such as comonomer incorporation or tacticity, different from the polymeric segment 32 or 32a. In step 4, the chain transfer occurs again involving catalysts C 'and C. The continued polymerization of both catalyst sites in step 5, forms new polymeric segments, 32b and 36a, also having different polymeric properties such as comonomer incorporation or tacticity. Each of these polymeric segments is joined by the rest of the two-center exchange agent, 34 to the polymeric segment 32a. Ending in step 6 results in the formation of three polymeric products, 38, 39, which are distinguishable based on the molecular weight as well as the presence of the two-center chain exchange agent residue, 34, in the polymeric products 38 and 40. In addition, products 38 and 39 are copolymers in pseudoblocks due to the presence of different polymeric regions formed by the respective catalysts C 'and C. An additional polymer formed only from catalyst C' or C (not shown) may also be present in the product mixture. .

[0049] In Figure 4 a variation of the previous process is illustrated, employing two catalysts C and C 'in the polymerization of ethylene, 1 and a C3-20 α-olefin (T = Ci-ιβ hydrocarbyl), 2 in the presence of a two-center exchange agent, 3, having a divalent linker group, L, linking two chain exchange portions, M ¹ and M ² . The exchange plots M ¹ and M ² have different affinities with respect to catalysts C and C '. In particular, M ¹ is more inclined to engage in polymer transfer with the

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32/130 catalyst C while M ² has a higher reactivity (increased exchange rate) with catalyst C '. In the various chain exchange steps (1) and (3), coupling between M ¹ and catalyst C as well as between M ² and catalyst C 'is illustrated. The trained technician will understand that the various steps illustrated can occur in any order. By also selecting catalysts C and C 'with respect to their ability or inability to incorporate comonomer (or conversely produce distinguishable polymers), the graduates will have distinct and the resulting product will be a copolymer in diblocks. In particular, a diblock copolymer can be readily prepared having a block of a very crystalline ethylene or propylene polymer (little or no incorporation) and the other of an amorphous ethylene or propylene copolymer (larger amount of comonomer incorporation).

polymer catalyst segments, 4 and 5, by their physical properties [0050] The trained technician will understand that employing multiple catalysts, multiple monomers, multiple exchange agents (including both CSA and MSA type) and / or multiple reactors or varying conditions reactor conditions, numerous reaction product conditions are attainable.

[0051] The polymeric product can be recovered by termination, such as by reaction with water or another source of protons, or functionalized, if desired, forming terminal groups vinyl, hydroxyl, silane, carboxylic acid, ester of carboxylic acid, ionomer, or other functional end groups, especially to replace the exchange agent

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33/130 of chain. Alternatively, the polymeric segments can be coupled with a polyfunctional coupling agent, especially a difunctional coupling agent such as tolylene diisocyanate, dichloro dimethyl silane or ethylene dichloride, and recovered.

[0052] The following schematic illustration shows the application of the previous techniques for the preparation of polymers with terminal functionalities in α, ω of low molecular weight, especially a, ω-diols or a, ω-dienes:

oxidation

MPr / í í

MPr. (C ₂ H ₄ ) _n -MPr <\ NCaHA, -MPr

HO- (C ₂ H ₄ ) _n - L— (CjHLOn - OH

displacement where a two-center MSA at α, ω, (PrM'LMpr) containing two metal sites, M ', such as Zn, joined by a divalent linker group, L (such as a hydrocarbilene group) and replaced with Pr groups , such as trimethylsilyl groups, which may optionally be linked to each other as indicated by broken lines, is added to an ethylene polymerization process. A polymer with two metallic terminations is formed in the reaction that can be converted by known techniques (such as oxidation or displacement) into the corresponding polymeric products with dihydroxyl or di-vinyl functionality using conventional processes. Appropriate techniques for converting metallized polymers via displacement reactions are disclosed in J. Am. Chem. Soc., 127, 10166-10167 (2005), and references cited within them. [0053] The trained technician will quickly understand that the previous process may employ an exchange agent

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34/130 multicentre initially containing 2, 3, 4, or even more active centers, resulting in the formation of polymeric mixtures containing some amount of a polymer that is approximately double, triple, quadruple, or another multiple of the molecular weight of the remaining polymer and a star or branched morphology.

[0054] Ideally, the chain exchange rate is equivalent or faster than the polymer termination rate, even up to 10 or even 100 times faster than the polymer termination rate and significant with respect to the polymerization rate. This allows for the formation of significant amounts of polymeric chains terminated with chain exchange agents and capable of continuous monomer insertion leading to significant amounts of the higher molecular weight polymer.

[0055] Selecting different exchange agents or mixing agents with a catalyst, changing the composition of comonomer, temperature, pressure, optional chain terminating agent such as H ₂ , or other reaction conditions in separate reactors or zones of a reactor operating under sealed flow conditions, polymeric products can also be prepared having segments of varying density or concentration of comonomer, monomer content, and / or other distinctive property. For example, in a typical process employing two continuous solution polymerization reactors connected in series and operating under different polymerization conditions, each of the resulting polymeric segments will have a relatively wide molecular weight distribution characteristic of typical olefinic coordination polymerization catalysts,

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35/130 preferably an Mw / Mn of 1.2 to 10, more preferably of 1.5 to 5.0, but will reflect different polymerization conditions of its formation. In addition, certain amounts of a conventional random copolymer coincident with the formation of the present polymeric composition can also be formed, resulting in a mixture of resins. If a relatively fast exchange agent is employed, a copolymer will be obtained having shorter block lengths but of a more uniform composition with little formation of random copolymer. By appropriate selection of both a catalyst and a multi-center exchange agent, one can obtain relatively pure mixtures of two polymers differing in molecular weight by approximately one whole value, copolymers containing relatively large blocks or segments approaching true block copolymers, or mixtures of the above with more random copolymers.

[0056] Highly desired polymeric compositions according to the present invention comprise a polyolefin, especially an ethylene copolymer and a C3-8 comonomer alone or mixed with an ethylene homopolymer or a propylene homopolymer, said composition having a distribution of distinct bimodal molecular weight, the largest molecular weight component having an Mw approximately twice or triple that of the lowest molecular weight component.

[0057] Suitable chain exchange agents, if used in addition to a multi-center exchange agent, include metal compounds or complexes of groups 1-13, preferably groups 1, 2, 12 or 13 of the Periodic Table of the Elements, containing at least one group

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36/130 hydrocarbyl of Ci_20z preferably aluminum, gallium or zinc compounds substituted by hydrocarbyl containing from 1 to 12 carbon atoms in each hydrocarbyl group, and reaction products thereof with a source of protons. Preferred hydrocarbyl groups are alkyl groups, preferably straight or branched C2-8 alkyl groups. The most preferred exchange agents for use in the present invention are trialkyl aluminum or dialkyl zinc compounds, especially triethyl aluminum, tri (isopropyl) aluminum, tri (isobutyl) aluminum, tri (n-hexyl) aluminum, tri (noctil) aluminum , triethyl gallium, or diethyl zinc. Additional suitable exchange agents include the reaction product or mixture formed by combining the above organometallic compound, preferably a tri (Ci-e alkyl) or di (Ci-β) zinc compound, especially triethyl aluminum, tri (isopropyl) ) aluminum, tri (isobutyl) aluminum, tri (nhexyl) aluminum, tri (n-octyl) aluminum, or diethyl zinc, with less than a stoichiometric amount (relative to the number of hydrocarbyl groups) of a secondary amine or hydroxyl compound, especially bis (trimethylsilyl) amine, terciobutyl (dimethyl) siloxane, 2-hydroxymethyl pyridine, di (npentyl) amine, 2,6-di (terciobutyl) phenol, ethyl (1-naphthyl) amine, bis (2,3, 6,7-dibenzo-1-aza-cyclopentanamine), or 2,6-diphenyl phenol. Desirably, sufficient amine or hydroxy reagent is used such that one hydrocarbyl group remains per metal atom. The main reaction products of the above highly desired combinations for use in the present invention as exchange agents are (n-octyl) aluminum di (bis (trimethylsilyl) amide), bis (dimethyl (terciobutyl) siloxide), isopropyl and n- octil aluminum aluminum

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37/130 di (pyridinyl-2-methoxide), isobutyl aluminum bis (dimethyl (terciobutyl) siloxane), isobutyl aluminum bis (di (trimethyl-silyl) amide), n-octyl aluminum di (pyridine-2-methoxide), isobutyl aluminum bis (di (n-pentyl) amide), n-octyl aluminum bis (2,6-ditherciobutyl phenoxide), n-octyl aluminum di (ethyl (1-naphthyl) amide), ethyl aluminum bis (terciobutyl dimethyl siloxide), ethyl aluminum di (bis (trimethylsilyl) amide), ethyl aluminum bis (2,3,6,7-dibenzo-l-azacyclopentanamide), n-octyl aluminum bis (dimethyl (terciobutyl) siloxide), (2,6-diphenyl phenoxide) ethyl zinc, and ethyl zinc terciobutoxy.

[0058] Preferred chain exchange agents have the highest polymer transfer rates as well as the highest transfer efficiencies (reduced incidences of chain termination). Such exchange agents can be used in low concentrations and still achieve the desired degree of exchange. Most desirably, chain exchange agents with a single exchange site are employed due to the fact that they decrease the effective molecular weight of the polymer thereby reducing the viscosity of the reaction mixture and consequently reducing operating costs. [0059] Multicentre exchange agents suitable for use here are compounds or complexes containing two or more chain exchange portions per molecule that are capable of forming reversible electronic interactions with polymer chains prepared by a coordination polymerization catalyst. In addition, the rest formed due to the loss of the chain exchange portions must be able to interact with an active catalyst composition, ultimately resulting in polymer growth in two or more.

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38/130 more sites from the rest. Preferred multicentre exchange agents are compounds corresponding to the formula: (M ') _m A in which M' is a chain exchange moiety, preferably a monovalent derivative of a chain exchange agent formed by separation of a linker group, A , in is an integer from 2 to 6, preferably 2 or 3. Preferred groups A are organic groups, especially inertly substituted hydrocarbon or hydrocarbon groups, most preferably alkali or alkali groups and inertly substituted derivatives thereof. A most preferred group A is C2-20 hydrocarbadiyl. Specific examples of suitable M 'groups include monovalent radicals containing Group 6-13 metal, especially radicals containing zinc or aluminum. Preferred M 'radicals are those of the formula -M (P ^g ) _p , where M is the metal, P ⁹ is an organic radical, and p is a number from 1 to 5 indicating the number of P ⁹ groups. The appropriate P ⁹ groups are hydrogen, halogen, hydrocarbyl, hydrocarbiloxy, dihydrocarbyl phosphide, tri (hydrocarbyl) silyl, halogen substituted hydrocarbyl, halogen substituted tri (hydrocarbyl) silyl, chelating derivatives containing Lewis base from the above, and chelating ligands from neutral Lewis base, such as tetrahydrofuran and acetyl acetonate.

[0060] Specific examples of the previous MSA's include: (1,2-ethylene) di (zinc chloride), (1,2-ethylene) di (zinc bromide), (1,2-ethylene) di (ethyl zinc) , (1,2ethylene) bis ((trimethyl) silyl zinc), (1,4-butylene) di (zinc chloride), (1,4-butylene) di (zinc bromide), (1,4butylene) di ( ethyl zinc), (1,4-butylene) bis ((trimethyl) silyl selected from dihydrocarbilamido,

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39/130 zinc), bis (1,2-ethylene di-zinc), bis (1,3-propylene dizinco), bis (1,4-butylene di-zinc), methyl tri (1,2-ethylene bromide) zinc), (1,2-ethylene) bis (aluminum dichloro), and (1,2-ethylene) bis (diethyl aluminum).

Catalysts [0061] Catalysts suitable for use here include any compound or combination of compounds that is adapted to prepare polymers of the desired composition or type. Both heterogeneous and homogeneous catalysts can be employed. Examples of heterogeneous catalysts include the well-known Ziegler-Natta compositions, especially Group 4 metal halides supported on mixed Group 2 metal halides and alkoxides and the well-known chrome or vanadium based catalysts. However, preferably for ease of use for the production of polymeric segments of narrow molecular weight in solution, the catalysts for use here are homogeneous catalysts comprising a relatively pure organometallic compound or metal complex, especially compounds or complexes based on metals selected from Groups 3- 15 or the Lanthanide series of the Periodic Table of the Elements.

[0062] For use here, preferred metal complexes include metal complexes from Groups 3 to 15 of the Periodic Table of Elements containing one or more delocalized π-linkers or multipurpose Lewis base ligands. Examples include metallocene, semi-metallocene, constricted geometry, and polyvalent pyridylamine, or other complexes with a poly-based base. Generally, complexes are represented by the formula: MK _k X _x Z _z or a dimer thereof, where M is a metal selected from Groups 3-15,

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40/130 preferably 3-10, more preferably 4-10, and most preferably from Group 4 of the Periodic Table of the Elements; at each occurrence, K is, independently, a group containing delocalized π electrons or one or more pairs of electrons through which K bonds to Μ, said group K containing up to 50 atoms not containing hydrogen atoms, optionally two or more groups K can be joined forming a bridge structure, and optionally one or more K groups can be linked to Z, X or both Z and X; at each occurrence, X is, independently, a monovalent anionic portion having up to 40 non-hydrogen atoms, optionally one or more groups X can join together thus forming a divalent or polyvalent anion group, and even optionally, one or more groups X and one or more Z groups can join together thus forming a portion that is both covalently linked to M and coordinated with it; at each occurrence, Z is, independently, a Lewis base donor ligand of up to 50 non-hydrogen atoms containing at least one unshared electron pair through which Z coordinates with M; k is an integer from 0 to 3; x is an integer from 1 to 4; z is an integer from 0 to 3; and the sum, k + x, is equal to the formal oxidation state of M.

[0063] Appropriate metal complexes include those containing 1 to 3 neutral or anionic linker groups linked by π, which can be anionic linker groups linked by non-cyclic or cyclic delocalized π. Examples of such π-linked groups are cyclic or non-cyclic diene and dienyl groups, conjugated or unconjugated, alkyl groups, benzene borate groups, phosphol, and arene groups. The term connected by π means that the group

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41/130 ligand is bonded to the transition metal by an electron sharing of a partially delocalized π bond.

[0064] Each atom in the delocalized π-linked group can be independently replaced by a radical selected from the group consisting of hydrogen, halogen, hydrocarbyl, halogenated hydrocarbyl, hydrocarbyl-substituted heteroatoms where the heteroatom is selected from Group 14-16 of the Periodic Table of the Elements, and such hydrocarbyl-substituted heteroatom radicals substituted by a portion containing Group 15 or 16 heteroatom. In addition, two or more such radicals may together form a fused ring system, including partially or completely hydrogenated fused ring systems , or they can form a metallocycle with the metal. Linear, branched and cyclic Ci_20z alkyl radicals, Ce-20 aromatic radicals, aromatic radicals substituted by alkyl of alkyl substituted by aryl of 0 ₇ -2ο · heteroatom substituted by hydrocarbyl include mono-, radicals within the term hydrocarbyl. di- and tri-substituted boron, silicon, germanium, nitrogen, phosphorus or oxygen where each hydrocarbyl group contains 1 to 20 carbon atoms. Examples include the N, N-dimethylamino, pyrrolidinyl, trimethyl silyl, triethyl silyl, terciobutyl dimethyl silyl, methyl di (terciobutyl) silyl, triphenyl germyl, and trimethyl germyl groups. Examples of parcels containing Group 15 or 16 heteroatom include amino, phosphine, alkoxy, or alkylthio or divalent derivatives thereof, for example, amide, phosphide, alkyleneoxy or alkylene thio groups, attached to the transition metal or to the lanthanide metal. , and connected to the group

C ₇ -20z θ radicals The radicals of

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42/130 hydrocarbyl, π-linked group, or heteroatom substituted by hydrocarbyl.

[0065] Examples of groups linked by π delocalized anionic groups include cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl, dihydro anthracenyl, hexahydro anthracenyl, decahydrohydrate and even hydroxyanhydrate derivatives, even as substituted hydroxy and anhydrous. , especially derivatives substituted by C11 hydrocarbyl or replaced by tris (C11 hydrocarbyl) silyl. Preferred anionic delocalized π-linked groups are cyclopentadienyl, pentamethyl cyclopentadienyl, tetramethyl cyclopentadienyl, tetramethyl silyl cyclopentadienyl, indenyl, 2,3-dimethyl indenyl, fluorenyl, 2-methyl indenyl, 2-methyl-indenyl, 4-phenyl-indyphenyl, 4-phenyl, methyl-4-phenyl, 3-phenyl octahydrofluorenyl, 1-indacenyl, 3pyrrolidine inden-1-yl, pentadienyl, 3,4 (cyclopenta (1) phenanthren-1-yl, and tetrahydroindenyl.

[0066] Benzyl borate binders are ionic binders that are analogues containing boron to benzene. They are previously known in the art and have been described by G. Herberich et al., In Organometallics, 14, 1, 471-480 (1995). The benzyl borate binders correspond to the formula:

in which R ¹ is selected from the group silyl, halogen or

R ¹ R ¹ inert substituent, preferably consisting of hydrogen, hydrocarbyl, germyl, said R ¹ having up to 20 atoms

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43/130 not counting hydrogen, and optionally two adjacent R ¹ groups can join. In complexes involving bivalent derivatives of such groups linked by delocalized π an atom of the same is linked via a covalent bond or a divalent group covalently linked to another atom of the complex thus forming a bridge system.

[0067] Phosphols are anionic ligands that are analogues containing phosphorus to a cyclopentadienyl group. They are previously known in the art having been described by WO 98/50392, and elsewhere. The preferred phosphol binders correspond to the formula:

in which R ¹ is as defined above.

[0068] The preferred transition metal complexes for use here correspond to the formula: MKkX _x Z _z , or a dimer thereof, in which: M is a Group 4 metal; K is a group containing delocalized π electrons through which K binds to Μ, said group K containing up to 50 atoms not containing hydrogen atoms, optionally two or more K groups can join together forming a bridge structure, and optionally one group K can bind to X or Z; at each occurrence, X is a monovalent anionic portion having up to 40 non-hydrogen atoms, optionally one or more groups X and one or more groups Z can join together thus forming a portion that is both covalently linked to M and coordinated with it; at each occurrence, Z is independently a Lewis base donor ligand of up to 50 non-hydrogen atoms containing at least one unshared electron pair

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44/130 through which Z coordinates with M; k is an integer from 0 to 3; x is an integer from 1 to 4; z is an integer from 0 to 3; and the sum, k + x, is equal to the formal oxidation state of M.

[0069] Preferred complexes include those containing either one or two K groups. The latter complexes include those containing a bridge group linking the two K groups. The preferred bridge groups are those corresponding to the formula (ER'2) _and in which E is silicon, germanium, tin, or carbon, in each occurrence R is, independently, hydrogen or a selected group of silyl, hydrocarbyl, hydrocarbiloxy and combinations thereof, said R 'even having carbon or silicon atoms, and e is from 1 to 8. Preferably, at each occurrence, R 'is, independently, methyl, ethyl, propyl, benzyl, terciobutyl, phenyl, methoxy, ethoxy or phenoxy.

[0070] Examples of complexes containing two K groups are compounds corresponding to the formulas:

in which: M is titanium, zirconium or hafnium, preferably zirconium or hafnium, in the formal oxidation state +2 or +4; at each occurrence R ³ is independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyan, halogen and combinations thereof, said R ³ having up to 20 non-hydrogen atoms, or adjacent R ³ groups together form one bivalent derivative (that is, a group

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45/130 hydrocarbadiil, siladiol or germadiila) thus forming a fused ring system, and in each occurrence X is, independently, an anionic linker group of up to 40 non-hydrogen atoms, or two X groups together form a bivalent anionic linker group of up to 40 non-hydrogen atoms or together are a conjugated diene having 4 to 30 non-hydrogen atoms linked by π electrons displaced to M, after which M is in the +2, and R ', E [ 0071] Examples of bridging linkers containing two π-linked groups: dimethyl bis (cyclopentadienyl) silane, dimethyl bis (tetramethyl cyclopentadienyl) silane, dimethyl bis (2-ethyl cyclopentadien-l-yl) silane, dimethyl bis (2terciobutyl cyclopentadien- 1-yl) silane, 2,2-bis (tetramethyl cyclopentadienyl) propane, dimethyl bis (inden-1-yl) silane, dimethyl bis (tetrahydro-1-yl) silane, dimethyl bis (fluoren1-yl) silane, dimethyl bis (tetrahydro fluoren-l-yl) silane, dimethyl bis (2-methyl-4-phenylinden-l-yl) silane, dimethyl bis (2methyl inden-1-yl) silane, dimethyl (cyclopentadienyl) (fluoren-lil) silane, dimethyl (cyclopentadienyl) (octahydrofluoren-1il) silane, dimethyl (cyclopentadienyl) (tetrahydrofluoren-1il) silane, (1, 1,2,2-tetramethyl) -1,2-bis (cyclopentadienyl) disilane, 1,2-bis (cyclopentadienyl) ethane, and dimethyl (cyclopentadienyl) -1- (fluoren-l-yl) methane.

The preferred groups X are selected from groups hydride, hydrocarbyl, silyl, germyl, halogenated hydrocarbyl, halogenated silyl, hydrocarbyl and amino hydrocarbyl, or two groups X together form a divalent derivative of a conjugated diene or together they form a conjugated diene bound by π neutral. The X groups

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46/130 most preferred are hydrocarbyl groups of Ci [0073]

Examples of metal complexes of the preceding formulas for use in the present invention include: dimethyl bis (cyclopentadienyl) zirconium, bis (cyclopentadienyl) zirconium, bis (cyclopentadienyl) zirconium, bis (cyclopentadienyl) zirconium, bis (cyclopentadienyl) zirconium, bis (cyclopentadienyl) zirconium , bis (cyclopentadienyl) zirconium, bis (cyclopentadienyl) zirconium, cyclopentadienyl) zirconium, dibenzyl methyl benzyl methyl phenyl diphenyl allyl methyl methoxide dimethyl chloride bis (pentamethyl dimethyl bis (pentamethyl cyclopentadienyl) titanium, methyl (inden) 2- (dimethylamino) benzyl) bis (indenyl) zirconium, trimethyl silyl bis (indenyl) zirconium, ethyl trimethyl silyl bis (tetrahydro indenyl) zirconium, methyl benzyl cyclopentadienyl) zirconium, dibenzyl cyclopentadienyl) zirconium, methyl bis (pentamethyl) methyloxide zirconium, cyclopentadienyl) zirconium, cyclopentadienyl) zirconium, cyclopentadienyl) zirconium, bis (pentamethyl bis (pentamethyl bis chloride (pentamethyl dimethyl bis (methyl ethyl d ibenzyl bis (butyl dimethyl bis (terciobutyl cyclopentadienyl) zirconium, cyclopentadienyl) zirconium, cyclopentadienyl) zirconium, cyclopentadienyl) zirconium, dimethyl bis (ethyl tetramethyl dibenzyl bis (methyl propyl dibenyl bis (trimethyl silyl bisethyl) dimethyl) allyl dimethyl silyl bis (tetramethyl cyclopentadienyl) titanium (III), dimethyl silyl bis (terciobutyl cyclopentadienyl) zirconium, dimethyl silyl bis (n-butyl dichloride

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47/130 cyclopentadienyl) zirconium, 2- (dimethylamino) benzyl methylene bis (n-butyl cyclopentadienyl) titanium (III), benzyl dimethyl silyl bis (indenyl) zirconium, dimethyl (dimethyl silyl) bis (2-methyl indenyl) zirconium , dimethyl (dimethyl silyl) bis (2methyl-4-phenyl indenyl) zirconium, dimethyl silyl bis (2-methyl indenyl) zirconium-1,4-butadiene, dimethyl silyl bis (2-methyl-4phenyl indenyl) zirconium (II) - 1,4-diphenyl-1,3-butadiene, dimethyl silyl bis (tetrahydro indenyl) zirconium (11) -1,4diphenyl-1,3-butadiene, dimethyl (dimethyl silyl) bis (tetramethyl cyclopentadienyl) zirconium, dimethyl (dimethyl silyl ) bis (fluorenyl) zirconium, bis (trimethyl silyl) (dimethyl silyl) bis (tetrahydro fluorenyl) zirconium, dibenzyl (isopropylidene) (cyclopentadienyl) (fluorenyl) zirconium, and dimethyl (dimethyl silyl) (tetramethyl cyclopentadienyl) (fluoridyl) zirconium).

[0074] An additional class of metal complexes used in the present invention corresponds to the previous formula: MK _k X _x Z _z , or a dimer thereof, in which Μ, K, X, x and z are as defined above, and Z is a substituent of up to 50 non-hydrogen atoms which together with K forms a metallocycle with M.

Preferred Z substituents include groups containing up to 30 non-hydrogen atoms comprising at least one atom that is oxygen, sulfur, boron or a member of Group 14 of the Periodic Table of the Elements directly linked to K, and a different, selected atom of the group consisting of nitrogen, phosphorus, oxygen or sulfur that is covalently linked to M.

[0076] More specifically this Group 4 metal complex class used in accordance with the present invention

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48/130 includes constrained geometry catalysts corresponding to the formula:

K ¹ —ΜΧχ in which: M is titanium or zirconium, preferably titanium in the formal oxidation state +2, +3, or +4; K ¹ is a delocalized π linker group optionally substituted with 1 to 5 R ² groups; at each occurrence R ² is independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyan, halogen and combinations thereof, said R ² having up to 20 non-hydrogen atoms, or adjacent R ² groups together form one bivalent derivative (i.e., hydrocarbadiyl, siladiyl or germadiyl group) thus forming a fused ring system; each X is a halogen, hydrocarbyl, hydrocarbiloxy or silyl group, said group having up to 20 non-hydrogen atoms, or two groups X together form a conjugated neutral C5-30 diene or a divalent derivative thereof; x is 1 or 2; Y is -O-, -S-, NR'-, -PR'-; and X 'is SiR' 2, CR ' ₂ , SiR' ₂ SiR ' ₂ , CR' ₂ CR ' ₂ , CR' = CR ', CR' ₂ SiR ' ₂ , or GeR' ₂ , with each occurrence R 'is, independently, hydrogen or a selected group of silyl, hydrocarbyl, hydrocarbiloxy and combinations thereof, said R' having up to 30 carbon or silicon atoms.

[0077] Specific examples of the metal constructs of previous constricted geometry include compounds corresponding to the formula:

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49/130 in which Ar is an aryl group of 6 to 30 atoms not counting hydrogen; at each occurrence R ⁴ is, independently, hydrogen, Ar, or a group other than Ar selected from hydrocarbyl, trihydrocarbil silyl, trihydrocarbil germyl, halide, hydrocarbiloxy, trihydrocarbil siloxy, bis (trihydrocarbil silyl) amino, di (hydrocarbil) amino, hydrocarbadiylamino, hydrocarbilimino, di (hydrocarbyl) phosphine, hydrocarbadiyl phosphine, hydrocarbyl sulfite, hydrocarbyl substituted with halogen, hydrocarbyl substituted with hydrocarbyloxy, hydrocarbyl substituted with trihydrocarbyl silyl, hydrocarbyl substituted with hydrocarbyl siloxy, hydrocarbyl substituted with bis (trihydrocarbyl) hydrocarbyl substituted with bis (trihydrocarbyl) substituted with di (hydrocarbyl) amino, hydrocarbyl amino, di (hydrocarbyl) phosphine, hydrocarbyl phosphine, hydrocarbyl hydrocarbyl hydrocarbyl or substituted hydrocarbyl substituted substituted substituted with with with hydrocarbyl sulfite, said group R ⁴ having up to 40 atoms not containing hydrogen atoms, and optionally two R ⁴ groups they can come together forming a fused polycyclic ring group; M is titanium; X 'is SiR ⁶ 2, CR ⁶ 2, SiR ⁶ 2SiR ⁶ 2, CR ⁶ = CR ⁶ , CR ⁶ 2SiR ⁶ 2,

BR ⁶ , BR ⁶ L, or GeR ⁶ 2; Y is -O-,

-NR ³

-PR ³

-NR ₂ , or

-PR ₂ ; at each occurrence R is, hydrocarbyl, trihydrocarbyl sily, or trihydrocarbyl sily hydrocarb, said R ⁵ having up to 20 atoms other than hydrogen, and optionally two groups R ⁵ or R ⁵ together with Y or Z form a ring system; at each occurrence R ⁶ is, independently, hydrogen or a selected member of hydrocarbyl, hydrocarbiloxy, silyl, halogenated alkyl, independently, halogenated aryl, -NR ⁵ 2, and combinations thereof, said R ⁶

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50/130 having up to 20 non-hydrogen atoms, and optionally two groups R ⁶ or R ⁶ together with Y or Z form a ring system; Z is a neutral diene or a monodentate or polyidentized Lewis base optionally linked to R ⁵ , R ⁶ , or X; X is hydrogen, a monovalent anionic linking group having up to 60 atoms not counting hydrogen, or two groups X joining together to form a divalent linking group; xélou2; ezéO, 1 or 2.

[0078] Preferred examples of the above metal complexes are cyclopentadienyl or indenyl groups substituted in both position 3 and 4 with an Ar group.

[0079] Examples of prior metal complexes include: titanium (3-phenyl-cyclopentadien-lil) dimethyl (terciobutyl starch) dichloride, dimethyl (3-phenyl-cyclopentadien-l-yl) dimethyl (tert-butyl starch) silane titanium, (3-phenyl- cyclopentadien-l-yl) dimethyl (terciobutyl starch) silane titanium (II) 1,4-diphenyl-1,3-butadiene, (3 (pyrrol-l-yl) cyclopentadien-l-yl) dimethyl (terciobutyl starch) silane titanium , dimethyl (3- (pyrrol-l-yl) cyclopentadien-lil) dimethyl (terciobutyl) starch titanium, (3- (pyrrol-lil) cyclopentadien-l-yl) dimethyl (terciobutyl starch) titanium (II) 1,4- diphenyl-1,3-butadiene, (3,4diphenyl-pyrrol-3-yl) cyclopentadien-l-yl) dimethyl (terciobutyl starch) silane titanium, dimethyl (3,4-diphenyl cyclopentadien-l-yl) dimethyl (tert-butyl butyl) ) titanium silane, (3,4-diphenyl cyclopentadien-1-yl) dimethyl (terciobutyl starch) titanium (II) 1,3-pentadiene silane, (3- (3-N, N-dimethylamino) phenyl) cyclopentadien-l-yl dichloride ) dimethyl (tert-butyl starch) titanium silane, dimethyl (3- (3 -N, Ndimethylamino) phenyl) cyclopentadien-1 Petition 870170056094, of 08/04/2017, p. 57/141

51/130 il) titanium (II (3-N, N-dimethylamino) phenyl) cyclopentadien-1yl) dimethyl (terciobutylamido) titanium (II) 1,4-diphenyl1,3-butadiene; (3- (4-methoxy phenyl) -4-methyl cyclopentadien-1-yl) dimethyl (terciobutyl starch) silane titanium, dimethyl (3- (4-methoxy phenyl) -4-methyl cyclopentadienyl-yl) dimethyl (terciobutyl starch) titanium silane, (3- (4-methoxy phenyl) -4-methyl cyclopentadien-1-yl) dimethyl (terciobutyl starch) titanium (II) 1,4-diphenyl-1,3-butadiene silane; (3-phenyl-4-methoxy cyclopentadien-l-yl) dimethyl (terciobutyl starch) silane titanium, dimethyl (3-phenyl-4-methoxy cyclopentadien-l-yl) dimethyl (terciobutyl starch) silane titanium, (3-phenyl- 4-methoxy cyclopentadien-lil) dimethyl (terciobutyl starch) silane titanium (II) 1,4-diphenyl1,3-butadiene; (3-phenyl-4- (N, Ndimethylamino) cyclopentadien-l-yl) dimethyl (terciobutyl starch) silane titanium, dimethyl (3-phenyl-4- (N, N-dimethylamino) cyclopentadien-l-yl) dimethyl ( terciobutyl starch) silane titanium, (3-phenyl-4- (N, N-dimethylamino) cyclopentadien-lil) dimethyl (terciobutyl starch) silane titanium (II) 1,4-diphenyl1,3-butadiene; 2-methyl- (3,4-di (4-methyl phenyl) cyclopentadien-1-yl) dimethyl (terciobutyl starch) silane titanium dichloride, 2-methyl- (3,4-di (4-methyl phenyl) cyclopentadien- 1-yl) dimethyl (terciobutyl) starch titanium, 2-methyl- (3,4-di (4-methyl phenyl) cyclopentadien-lil) dimethyl (terciobutyl starch) titanium (II) 1,4-diphenyl1,3-butadiene; ((2,3-diphenyl) -4- (N, N-dimethylamino) cyclopentadien-1-yl) dimethyl (terciobutylamido) silane titanium, dimethyl ((2,3-diphenyl) -4- (N, N-dimethylamino) cyclopentadien- l-yl) dimethyl (terciobutyl starch)

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52/130 titanium silane, ((2,3-diphenyl) -4- (N, Ndimethylamino) cyclopentadien-1-yl) dimethyl (terciobutyl starch) titanium (II) 1,4-diphenyl-1,3-butadiene; (2,3,4-triphenyl-5-methyl cyclopentadien-1-yl) dimethyl (terciobutyl starch) silane titanium, dimethyl (2,3,4-triphenyl-5methyl cyclopentadien-l-yl) dimethyl (tert-butyl starch) silane titanium , (2,3,4-triphenyl-5-methyl cyclopentadien-lil) dimethyl (terciobutyl starch) titanium (II) 1,4-diphenyl1,3-butadiene; (3-phenyl-4-methoxy cyclopentadienl-yl) dimethyl (terciobutyl starch) silane titanium, dimethyl (3-phenyl-4-methoxy cyclopentadien-l-yl) dimethyl (terciobutyl starch) silane titanium, (3-phenyl-4-methoxy cyclopentadien -yl) dimethyl (tert-butyl starch) silane titanium (II) 1,4-diphenyl1,3-butadiene; (2,3-diphenyl-4-infant) cyclopentadien-l-yl) dimethyl (terciobutyl starch) silane titanium, dimethyl (2,3-diphenyl-4- (n-butyl) cyclopentadien-lil) dimethyl (terciobutyl starch) silane titanium, (2,3-diphenyl-4 (n-butyl) cyclopentadien-1-yl) dimethyl (terciobutyl starch) silane titanium (II) 1,4-diphenyl-1,3-butadiene; (2,3,4,5tetra-phenyl cyclopentadien-1-yl) dimethyl (terciobutyl starch) silane titanium, dimethyl (2,3,4,5-tetra-phenyl cyclopentadienyl-yl) dimethyl (tert-butyl starch) silane titanium, ( 2,3,4,5tetra-phenyl cyclopentadien-1-yl) dimethyl (terciobutyl starch) silane titanium (II) 1,4-diphenyl-1,3-butadiene.

[0080] Additional examples of metal complexes suitable for use here are polycyclic complexes corresponding to the formula:

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53/130

where M is titanium in the formal oxidation state +2, +3 or + 4; at each occurrence R ⁷ is, independently, hydride, hydrocarbyl, silyl, germyl, halide, hydrocarbiloxy, hydrocarbyloxy, di (hydrocarbyl) amino, substituted replaced with hydrocarbyl silyl, amino hydrocarbyl, phosphine di (hydrocarbyl), phosphine hydrocarbyl, hydrocarbyl sulfite, hydrocarbyl substituted with halogen, hydrocarbyl substituted with hydrocarbiloxy, hydrocarbyl substituted with trihydrocarbyl sily, hydrocarbyl substituted with hydrocarbyl siloxy, hydrocarbyl substituted with hydrocarbyl silyl, hydrocarbyl substituted with phosphine di (hydrocarbyl), hydrocarbyl substituted with hydrocarbyl phosphine hydrocarbene, , or hydrocarbyl hydrocarbyl sulfite, said group R ⁷ having up to 40 atoms not counting hydrogen atoms, and optionally two groups R ⁴ can be joined to form a divalent derivative; R ⁸ is a divalent hydrocarbilene or substituted hydrocarbilene group forming a fused system with the rest of the metal complex, said R ⁸ containing from 1 to 30 atoms not containing hydrogen; X ^a is a bivalent portion, or a portion comprising a σ bond and two pairs of neutral electrons capable of forming a coordinated covalent bond with Μ, said X ^a comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and also comprising

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54/130 nitrogen, phosphorus, sulfur or oxygen; X is a monovalent anionic linker group having up to 60 atoms exclusive to the class of linkers which are linker groups by cyclic delocalized π linkage and optionally two groups X together form divalent linker groups; at each occurrence Z is, independently, a neutral binding compound having up to 20 atoms; xéO, lou2; ezé zero or 1.

[0081] Preferred examples of such complexes are 3-phenyl substituted s-indecenyl complexes corresponding to

formulas:

replaced with 2,3-dimethyl

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55/130

[0082] Additional examples of metal complexes that are usefully employed in accordance with the present invention include those of the formulas:

Si (CH ₃ > 2 \ c (CH ₃ ) 3

TK

CHr ^ O

-Si (CH3) ₂ \

NG (CH3) ₃ cm-cH // ¹

C ₆ H ₅ HC CHCsHs'

SY (CH3) _{2 Tr} ? NC (CH ₃ > 3 / \ ch ₃ ^z ch ₃

--Si (CH ₃ ) ₂ \

NC (CH ₃ ) ₃ CH; CH // X

CeHsHC CHC ₆ H ₅ '

-Si (CH ₃ ) 2 \

NC (CH ₃ ) ₃

Tr ^

CH ₃ [0083] Methylene-1,8-dihydrodibenzo ethyl) dimethyl silanamide metal complexes

Si (CH ₃ ) ₂ \ c (CH3) ₃

TK / \

Specific CHg ⁷ CH ₃ include: (8 [e, h] azulene-1-yl) -N- (1,1-dimethyl titanium (II) 1,4-diphenyl-1,3butadiene, (8-methylene-1, 8-dihydrodibenzo [e, h] azulen-l-yl) -N (1,1-dimethyl ethyl) dimethyl silanamide titanium (II) 1,3 pentadiene, (8-methylene-1,8-dihydrodibenzo [e, h] azulen -l-il) Petition 870170056094, of 08/04/2017, page 62/141

56/130

Ν- (1,1-dimethyl ethyl) dimethyl silanamide titanium (III) 2- (N, Ndimethylamino) benzyl, (8-methylene-1,8-dihydrodibenzo [e, h] azulene-l-yl) -N- ( 1,1-dimethyl ethyl) dimethyl

titanium (IV) silanamide, dimethyl (8- -methylene-1,8-dihydrodibenzo [e, h] azulene-l-yl) -N- (1,1-dimethyl ethyl) dimethyl silanamide titanium (IV), dibenzyl (8- -methylene-1,8-dihydrodibenzo [e, h] azulene-l-yl) -N- (1,1-dimethyl ethyl) dimethyl silanamide titanium (IV), (8-difluoro methylene-1,8-dihydrodibenzo [e, h] azulene-l-yl) -N- (1,1-dimethyl ethyl) dimethyl silanamide

titanium (II) 1,4-diphenyl-1,3-butadiene, (8-difluoro methylene1,8-dihydrodibenzo [e, h] azulene-l-yl) -N- (1,1-dimethyl ethyl) dimethyl silanamide titanium (II) 1,3-pentadiene, 2- (N, Ndimethylamino) benzyl (8-difluoro methylene-1,8-dihydrodibenzo [e, h] azulene-1-yl) -N- (1,1-dimethyl ethyl) titanium (III) dimethyl silanamide, (8-difluoro methylene-1,8dihydrodibenzo [e, h] azulene-l-yl) -N- (1,1-dimethyl ethyl) dimethyl titanium (IV) dichloride, dimethyl (8 -difluoro methylene-1,8dihydrodibenzo [e, h] azulene-l-yl) -N- (1,1-dimethyl ethyl) dimethyl silanamide titanium (IV), dibenzyl (8-difluoro methylene-1,8dihydrodibenzo [e, h ] azulen-l-yl) -N- (1,1-dimethyl ethyl) dimethyl

titanium (IV) silanamide, (8- methylene-1,8-dihydrodibenzo [e, h] azulene-2-yl) -N- (1,1-dimethyl ethyl) dimethyl silanamide

titanium (II) 1,4-diphenyl-1,3-butadiene, (8-methylene-1,8-dihydrodibenzo [e, h] azulene-2-yl) -N- (1,1-dimethyl ethyl) dimethyl silanamide titanium ( II) 1,3-pentadiene, 2- (N, N-

dimethylamino) benzyl (8- -methylene-1,8-dihydrodibenzo [e, h] azulen-2-yl) -N- (1,1-dimethyl ethyl) dimethyl silanamide titanium (III), dichloride (8- methylene-1,8-dihydrodibenzo [e, h] azulene-2-yl) -N- (1,1-dimethyl ethyl) dimethyl silanamide titanium (IV), dimethyl (8- methylene-1,8-dihydrodibenzo

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57/130 [e, h] azulene-2-yl) -N- (1,1-dimethyl ethyl) dimethyl silanamide titanium (IV), dibenzyl (8-difluoro methylene-1,8-dihydrodibenzo ethyl) dimethyl silanamide methylene- 1,8-dihydrodibenzo ethyl) dimethyl silanamide ethyl) dimethyl silanamide (8-difluoro methylene-1,8 [e, h] azulene-2-yl) -N- (1,1-dimethyl titanium (IV), (8- difluoro [e, h] azulene-2-yl) -N- (1,1-dimethyl titanium (II) 1,4-diphenyl-1,3-butadiene, (8-difluoro methylene1,8-dihydrodibenzo [e, h ] azulen-2-yl) -N- (1,1-dimethyl ethyl) dimethyl silanamide titanium (II) 1,3-pentadiene, 2- (N, Ndimethylamino) benzyl (8-difluoro methylene-1,8-dihydrodibenzo [ e, h] azulen-2-yl) -N- (1,1-dimethyl titanium (III), dihydrodibenzo dichloride [e, h] azulene-2-yl) -N- (1,1-dimethyl ethyl) dimethyl titanium (IV) silanamide, dimethyl (8-difluoro methylene-1,8 dihydrodibenzo [e, h] azulene-2-yl) -N- (1,1-dimethyl ethyl) dimethyl titanium (IV) silanamide, dibenzyl (8-difluoro methylene-1,8dihydrodibenzo [e, h] azulene-2-yl) -N- (1,1-dimethyl ethyl) dimethyl silanamide titanium (IV), and mixtures thereof, especially mixtures of position isomers.

[0084] Additional illustrative examples of metal complexes for use according to the present invention correspond to the formulas:

or

where M is titanium in the formal oxidation state +2, +3 or +4; T is -NR ⁹ - or -O-; R ⁹ is hydrocarbyl, silyl, germyl, dihydrocarbyl boryl, or halogenated hydrocarbyl or up to 10

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58/130 atoms not counting hydrogen; in each occurrence R ¹⁰ is, independently, hydrogen, hydrocarbyl, trihydrocarbyl silyl, trihydrocarbyl sily hydrocarbyl, germyl, halide, hydrocarbiloxy, hydrocarbyl siloxy, hydrocarbyl silyl amino, di (hydrocarbyl) amino, hydrocarbyl amino, di (hydrocarbyl) phosphine, phosphine hydrocarbyl , hydrocarbyl sulfite, hydrocarbyl substituted with halogen, hydrocarbyl substituted with hydrocarbiloxy, hydrocarbyl substituted with silyl, hydrocarbyl substituted with hydrocarbyloxy, hydrocarbyl substituted with hydrocarbyl amino, substituted with di (hydrocarbyl) amino, hydrocarbyl hydrocarbyl substituted hydrocarbyl substituted with hydrocarbyl substituted amino, with phosphine dihydrocarbyl, phosphine hydrocarbyl or hydrocarbyl substituted with hydrocarbyl sulfite, said group R ¹⁰ having up to 40 atoms not containing hydrogen atoms, and optionally two or more adjacent R ¹⁰ groups can form a bivalent derivative thus forming a divalent derivative casting ring saturated or unsaturated; X ^a is a divalent portion lacking delocalized π electrons, or such portion comprising a σ bond and a neutral electron pair capable of forming a coordinated covalent bond with Μ, said X ^a comprising boron, or a member of Group 14 in the Table Periodic of the Elements, and also comprising nitrogen, phosphorus, sulfur or oxygen; X is a monovalent anionic linker group having up to 60 atoms exclusive to the class of ligands which are cyclic π bonded linker groups linked to M via delocalized π electrons or two groups X together form a bivalent anionic linker group; on each

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Occurrence Z is, independently, a neutral binding compound having up to 20 atoms; x is 0, 1, 2, or 3; ezéOoul.

Most preferably T is = N (CH3), H is halogen or hydrocarbyl, x is 2, X ^a is dimethyl silane, z is 0, and at each occurrence R ¹⁰ is hydrogen, hydrocarbyl group, hydrocarbiloxy, amino dihydrocarbyl, amino hydrocarbyl, hydrocarbyl group substituted with amino dihydrocarbil, or hydrocarbyl group substituted with amino hydrocarbilene of up to 20 atoms not counting hydrogen, and optionally two R ¹⁰ groups can join together.

[0085] Illustrative metal complexes of the previous formulas that can be used in the practice of the present invention further include the following compounds: (terciobutyl starch) dimethyl- [6,7] benzo- [4,5: 2 ', 3'] (1- methyl isoindole) - (3H) -inden-2-yl) titanium (II) 1,4-diphenyl-1,3-butadiene, (terciobutylamido) dimethyl- [6,7] benzo [4,5: 2 ', 3' ] (1-methyl isoindole) - (3H) -inden-2-yl) titanium (II) 1,3-pentadiene, 2- (N, N-dimethylamino) benzyl (terciobutyl starch) dimethyl- [6,7] benzo - [4,5: 2 ', 3'] (1-methyl isoindole) - (3H) -inden-2-yl) titanium (III) silane, dimethyl- (6,7] benzo- [tert-butylamido) dichloride 4,5: 2 ', 3'] (1-methyl isoindole) - (3H) -inden-2-yl) titanium (IV) silane, dimethyl (terciobutyl starch) dimethyl- [6,7] benzo- [4,5 : 2 ', 3'] (1-methyl isoindole) - (3H) -inden-2-yl) titanium (IV) silane, dibenzyl (terciobutyl starch) dimethyl- [6,7] benzo- [4,5: 2 ' , 3 '] (1-methyl isoindole) - (3H) -inden-2-yl) titanium (IV) silane, bis (trimethyl silyl) (terciobutyl starch) dimethyl- [6, 7] benzo- [4,5: 2 ', 3'] (1methyl isoindole) - (3H) -inden-2-yl) silane tit uranium (IV), (cyclohexylamino) dimethyl- [6,7] benzo- [4,5: 2 ', 3'] (1-methyl isoindole) (3H) -inden-2-yl) titanium (II) silane 1 , 4-diphenyl-1,3-butadiene,

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60/130 (cyclohexylamino) dimethyl- [6,7] benzo- [4,5: 2 ', 3'] (1-methyl isoindole) - (3H) -inden-2-yl) titanium (II) silane 1,3-pentadiene, 2- (N, N-dimethylamino) benzyl (cyclohexylamino) dimethyl [6.7] benzo- [4,5: 2 ', 3'] (1-methyl isoindole) - (3H) -inden-2yl) titanium (III) silane, (cyclohexylamino) dimethyl- [6,7] benzo- [4,5: 2 ', 3'] (1-methyl isoindole) - (3H) -inden2 -yl) titanium (IV) silane, dimethyl (cyclohexylamino) dimethyl [6,7] benzo- [4,5: 2 ', 3'] (1-methyl isoindole) - (3H) -inden-2yl) silane titanium (IV), dibenzyl (cyclohexylamino) dimethyl [6.7] benzo- [4,5: 2 ', 3'] (1-methyl isoindole) - (3H) -inden-2yl) silane titanium (IV) , bis (trimethyl silyl) (cyclohexylamino) dimethyl- [6.7] benzo- [4,5: 2 ', 3'] (1-methyl isoindole) - (3H) -inden2-yl) titanium (II ), (terciobutylamino) di (pmethylphenyl) [6.7] benzo- [4,5: 2 ', 3'] (1-methyl isoindole) - (3H) inden-2-yl) titanium (II) 1, 4-diphenyl-1,3-butadiene, (terciobutylamino) di (p-methylphenyl) [6,7] benzo- [4,5: 2 ', 3'] (1 methyl isoindole) - (3H) -inden-2- il) titanium (II) 1,3 pentadiene silane, 2- (N, N-dimethyl lamino) benzyl (terciobutylamino) di (p-methylphenyl) [6,7] benzo- [4,5: 2 ', 3'] (1-methyl isoindole) (3H) -inden-2-yl) silane titanium (III ), (tert-butylamino) di (p-methylphenyl) [6,7] benzo- [4,5: 2 ', 3'] (1methyl isoindole) - (3H) -inden-2-yl) silane titanium (IV) dichloride ), dimethyl (terciobutylamino) di (p-methylphenyl) [6.7] benzo- [4,5: 2 ', 3'] (1methyl isoindole) - (3H) -inden-2-yl) titanium (IV) silane , dibenzyl (terciobutylamino) di (p-methylphenyl) [6,7] benzo- [4,5: 2 ', 3'] (1methyl isoindole) - (3H) -inden-2-yl) titanium (IV) silane, bis (trimethyl silyl) (terciobutylamino) di (pmethylphenyl) [6,7] benzo- [4,5: 2 ', 3'] (1-methyl isoindole) - (3H) inden-2-yl) silane titanium (IV ), (cyclohexylamido) di (pmethylphenyl) [6,7] benzo- [4,5: 2 ', 3'] (1-methyl isoindole) - (3H) Petition 870170056094, of 08/04/2017, p. . 67/141

61/130 inden-2-yl) titanium (II) 1,4-diphenyl-1,3-butadiene, (cyclohexylamido) di (p-methylphenyl) [6,7] benzo- [4,5: 2 ', 3'] (1methyl isoindole) - (3H) -inden-2-yl) titanium (II) 1,3-pentadiene, 2- (N, N-dimethylamino) benzyl (cyclohexylamido) di (p-methylphenyl) [6 , 7] benzo- [4,5: 2 ', 3'] (1-methyl isoindole) - (3H) -inden-2-yl) titanium (III) silane, di (p- (cyclohexylamido) dichloride methylphenyl) [6,7] benzo- [4,5: 2 ', 3'] (1methyl isoindol) - (3H) -inden-2-yl) titanium (IV), dimethyl (cyclohexylamido) di (p -methylphenyl) [6,7] benzo- [4,5: 2 ', 3'] (1methyl isoindole) - (3H) -inden-2-yl) silane titanium (IV), dibenzyl (cyclohexylamido) di ( p-methylphenyl) [6,7] benzo- [4,5: 2 ', 3'] (1methyl isoindole) - (3H) -inden-2-yl) titanium (IV) silane, and bis (trimethyl silyl) ( cyclohexylamido) di (pmethylphenyl) [6.7] benzo- [4,5: 2 ', 3'] (1-methyl isoindole) - (3H) inden-2-yl) silane titanium (II).

[0086] Illustrative Group 4 metal complexes that can be employed in the practice of the present invention further include: dimethyl (terciobutyl starch) (1,1-dimethyl-2,3,4,9,10-T | 1,4,5 , 6,7,8-hexahydronaphthalenyl) dimethyl silane titanium, dimethyl (terciobutyl starch) (1, 1, 2,3-tetramethyl-2,3, 4, 9, 10-T | 1,4,5,6,7, 8-hexaidronaftalenil) dimethyl silane titanium dibenzyl (terciobutilamido) (tetramethyl-η ⁵ -cyclopentadienyl) dimethyl silane titanium dimethyl (terciobutilamido) (tetramethyl- ? | ⁵ -cyclopentadienyl) dimethyl silane titanium dimethyl (terciobutilamido) (tetramethyl-η ⁵ -cyclopentadienyl ) -1,2-ethanediyl titanium, dimethyl (terciobutyl starch) (tetramethyl-T | ⁵ -indenyl) dimethyl silane titanium, 2- (dimethylamino) (terciobutyl starch) (tetramethyl-η ⁵ cyclopentadienyl) dimethyl silane titanium (III), ally ( terciobutyl starch) (tetramethyl-T | ^5- cyclopentadienyl) dimethyl

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1,4-diphenyl-1,3-butadiene, indenyl) dimethyl silane titanium (III), 2,4-dimethyl pentadienyl (terciobutyl starch) (tetramethyl-q ^5- cyclopentadienyl) dimethyl titanium (III), (terciobutyl starch) ( tetramethyl-η ⁵ cyclopentadienyl) dimethyl titanium (II) 1,4-diphenyl-1,3-butadiene (tert-butyl starch) (tetramethyl-η ⁵ cyclopentadienyl) dimethyl titanium (II) 1,3-pentadiene, (tert-butylamido) (2- methyl indenyl) dimethyl silane titanium (II) (terciobutyl starch) (2-methyl titanium (II) 2,4-hexadiene, (terciobutyl starch) (2-methyl indenyl) dimethyl silane titanium (IV)

2.3- dimethyl-1,3-butadiene, (terciobutyl starch) (2-methyl indenyl) dimethyl silane titanium (IV) isoprene, (terciobutyl starch) (2-methyl indenyl) dimethyl silane titanium (IV)

1.3- butadiene, (tert-butyl starch) (2,3-dimethyl indenyl) dimethyl silane titanium (IV) 2,3-dimethyl-1,3-butadiene, (terciobutyl starch) (2,3-dimethyl indenyl) dimethyl titanium (IV) isoprene, dimethyl (tert-butyl starch) (2,3-dimethyl indenyl) dimethyl silane (tert-butyl starch) (2,3-dimethyl titanium (IV), indenyl) dimethyl dibenzyl silane titanium (IV), (terciobutyl starch) (2,3-dimethyl indenyl ) titanium (IV) dimethyl silane (IV) 1,3-butadiene, (2,3-dimethyl indenyl) titanium (II) dimethyl silane (1,3) pentadiene, (terciobutyl starch) (2,3-dimethyl indenyl) dimethyl titanium (II) ) 1,4-diphenyl-1,3-butadiene, (tert-butyl starch) (2-methyl indenyl) dimethyl silane titanium (II) 1,3-pentadiene, dimethyl (terciobutyl starch) (2-methyl indenyl) dimethyl silane titanium (IV), dibenzyl (terciobutyl starch) (2-methyl indenyl) dimethyl silane titanium (IV), (terciobutyl starch) (2 methyl-4-phenyl indenyl) dimethyl silane titanium (II) 1,4-diphenyl1,3-butadiene, (terciobutyl starch) (2-methyl -4-phenyl

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63/130 indenyl) dimethyl silane titanium (II) 1,3-pentadiene, (terciobutyl starch) (2-methyl-4-phenyl indenyl) dimethyl silane titanium (II) 2,4-hexadiene, (terciobutyl starch) (tetramethyl-η ⁵ cyclopentadienyl) dimethyl titanium (IV) 1,3-butadiene, (terciobutyl starch) (tetramethyl-T | ^5- cyclopentadienyl) titanium (IV) 2,3-dimethyl-1,3-butadiene, (tert-butyl starch) (tetramethyl-) T | ^5- cyclopentadienyl) dimethyl silane titanium (IV) isoprene, (terciobutyl starch) (tetramethylT | ^5- cyclopentadienyl) dimethyl silane titanium (II) 1,4-dibenzyl1,3-butadiene, (terciobutyl) (tetramethyl-ien ⁵ cyclopentadiene) titanium (II) dimethyl silane 2,4-hexadiene, (terciobutyl starch) (tetramethyl-T | ^5- cyclopentadienyl) titanium (II) 3-methyl-1,3-pentadiene, dimethyl (tert-butyl starch) (2,4-dimethyl) pentadien-3-yl) dimethyl silane titanium, dimethyl (terciobutyl starch) (6,6-dimethyl cyclohexadienyl) dimethyl silane titanium, dimethyl (terciobutyl starch) (1,1-l-dimethyl-2,3,4,9,10-η- 1,4,5,6,7,8 naphthalen- 4-yl) dimethyl silane titanium, dimethyl (terciobutyl starch) (1,1,2,3-tetramethyl-2,3,4,9,10-η1,4,5,6,7,8-hexahydro-naphthalen-4- il) dimethyl silane titanium, dimethyl (terciobutyl starch) (tetramethyl-η ⁵ cyclopentadienyl) methyl phenyl silane titanium (IV), (terciobutyl starch) (tetramethyl-T | ^5- cyclopentadienyl) methyl phenyl silane titanium (II) 1,4-diphenyl-1,1-butadiene, dimethyl 1- (terciobutyl starch) -2- (tetramethyl-η ⁵ cyclopentadienyl) ethanediyl titanium (IV), and 1 (terciobutyl starch) -2- (tetramethyl-T | ^5- cyclopentadienyl) ethanediyl titanium (IV) 1,4-diphenyl-1,1-butadiene.

[0087] Other delocalized π bond complexes, especially those containing other Group 4 metals,

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64/130 will certainly become obvious to those trained in the art, and are disclosed among other places at: WO 03/78480, WO 03/78483, WO 02/92610, WO 02/02577, US 2003/0004286 and ^and in U.S. patent No s 6,515,155, 6,555,634, 6,150,297, 6,034,022, 6,268,444, 6,015,868, 5,866,704, and

5,470,993.

[0088] Additional examples of metal complexes that are usefully employed here include polyvalent Lewis base compounds corresponding to the formulas:

T * ⁵ / X _bh . (R) _g —X ”Y- (R ^b ) f

M i ^b bh

OR

T * (R ^b ) _g —x ^b xz ^M rb fyb fh ^z f preferably

Z / Λ

Y— (R ^b ') g

M 'b L _h ,

Z (R ^b ) g — x ⁶ Yh-CR ''') *

M

L ^b b h'-l, or γ— (R ^b ') g;

M

T b yb b h'-l ^Z f in which T ^b is a bridge-forming group, preferably containing 2 or more atoms other than hydrogen; each X ^b and Y ^b are independently selected from the group consisting of nitrogen, sulfur, oxygen and phosphorus, more preferably both X ^k and nitrogen; in each occurrence R are, independently, hydrogen or

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65/130 C1-50 hydrocarbyl groups optionally containing one or more heteroatoms or inertly substituted derivatives thereof. Non-limiting examples of suitable R ^b and R ^b 'groups include alkyl, alkenyl, aryl, aralkyl, (poly) alkylaryl and cycloalkyl groups, as well as derivatives thereof substituted with nitrogen, phosphorus, oxygen and halogen. Specific examples of suitable R ^b and R ^b 'groups include methyl, ethyl, isopropyl, octyl, phenyl, 2,6-dimethyl-phenyl, 2,6-di (isopropyl) phenyl, 2,4,6-trimethyl-phenyl, pentafluorophenyl, 3,5-trifluoromethylphenyl, and benzyl; g is 0 or 1; M ^b is a metallic element selected from Groups 3 to 15, or from the Lanthanide series of the Periodic Table of Elements. Preferably, M ^b is a Group 3-13 metal, more preferably M ^b is a Group 4-10 metal; L ^b is a monovalent, bivalent, or trivalent anionic ligand containing from 1 to 50 atoms, not counting hydrogen. Examples of suitable L ^b groups include halide, hydride, hydrocarbyl, hydrocarbiloxy, di (hydrocarbyl) starch, hydrocarbyl starch, di (hydrocarbyl) phosphide; hydrocarbon sulfoxide; hydrocarbiloxy, tri (hydrocarbil silyl) alkyl, and carboxylates. The most preferred L ^b groups are alkyl CI_ 20 / C ₇ -20 aralkyl / θ chloride; h is an integer from 1 to 6, preferably from 1 to 4, more preferably from 1 to 3, and j is 1 or 2, with the value hxj selected to provide load balancing; Z ^b is a neutral linker group coordinated to M ^b , and containing up to 50 atoms not counting hydrogen. Preferred Z ^b groups include aliphatic and aromatic amines, phosphines, and ethers, alkenes, alkadiene, and inertly substituted derivatives thereof. Suitable inert substituents include halogen, alkoxy, aryloxy, carbonyl alkoxy,

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66/130 aryloxy carbonyl, di (hydrocarbyl) amine, tri (hydrocarbyl) silyl, and nitrile. Preferred Z ^b groups include triphenyl phosphine, tetrahydrofuran, pyridine, and 1,4diphenyl-butadiene; f is an integer from 1 to 3; two or three of T ^b , R ^b and R ^b 'can be joined to form a single or multi-ring structure;

----- indicates any form of electronic interaction comprising an effective electrostatic attraction, especially coordinated or covalent bonds, including multiple bonds; the arrows mean coordinated connections; and dashed lines indicate optional double bonds. [0089] In an embodiment, it is preferred that R ^b has relatively low steric impedance with respect to X ^b . In this embodiment, the most preferred R ^b groups are normal chain alkyl groups, normal chain alkenyl groups, branched chain alkyl groups in which the closest branch point is at least 3 atoms removed from X ^b , and derivatives thereof replaced with halogen, amino dihydrocarbyl, alkoxy or trihydrocarbyl silyl. The most preferred R ^b groups in this embodiment are C 1-6 normal chain alkyl groups.

[0090] In this embodiment, at the same time R ^b 'preferably has relatively high steric impedance with respect to Y ^b . Non-limiting examples of R ^b 'groups suitable for this incorporation include alkyl or alkenyl groups containing one or more secondary or tertiary carbon centers, cycloalkyl, aryl, alkaryl groups, aliphatic or aromatic heterocyclic groups, inorganic or organic cyclic, polymeric or oligomeric groups , and derivatives thereof substituted with halogen, dihydrocarbil

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67/130 amino, alkoxy or trihydrocarbil silyl. In this embodiment, the preferred R ^b 'groups contain from 3 to 40, more preferably from 3 to 30, and most preferably from 4 to 20 atoms not containing hydrogen and are branched or cyclic.

[0091] Examples of preferred T ^b groups are structures corresponding to the following formulas:

\ _

C — C // \ _Z C — Si

Λ // (R ⁶ )! / (^ 2 (R ^d ) 2

C— Ge _ζ σ02 Λκί,. (R'h c-si .P - c .c— '?

in which each preferably

R ^d is a methyl, ethyl, \ / OU / f hydrocarbyl of C1-10 / n-propyl, isopropyl, terciobutyl, phenyl, 2,6-dimethyl-phenyl, benzyl, or tolyl.

Each is C1-10 hydrocarbyl, preferably methyl, ethyl, n-propyl, isopropyl, terciobutyl, phenyl, 2,6-dimethyl-phenyl, benzyl, or tolyl. In addition, two or more R ^d or R ^{e groups} , or mixtures of R ^d or R ^{e groups} can together form a polyvalent derivative of a hydrocarbyl group, such as 1,4-butylene, 1,5-pentylene, or a group heterohydrocarbyl or polyvalent multicyclic fused ring hydrocarbyl, such as naphthalene-1,8-diyl.

[0092] Preferred examples of the preceding multipurpose Lewis base complexes include:

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R ^J R ^rf

in which each occurrence of R ^d 'is independently selected from the group consisting of hydrogen and C1-50 hydrocarbyl groups optionally containing one or more hetero atoms, or derivatives thereof, substituted inertly, or optionally, two adjacent R ^d ' groups together they can form a bivalent bridge-forming group; d 'is 4; M ^b 'is a Group 4 metal, preferably titanium or hafnium or a group 10 metal, preferably Ni or Pd; L ^{b <} is a monovalent linker of up to 50 atoms not containing hydrogen, preferably halide or hydrocarbyl, or two groups R ^d 'together are a divalent or neutral linker group, preferably a C2-50 hydrocarbene / hydrocarbadiyl or diene group.

[0093] The polyvalent Lewis base complexes for use in the present invention include especially metal derivatives

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69/130 of Group 4, especially hafnium derivatives of hydrocarbilamine-substituted heteroaryl compounds corresponding to the formula:

, T * in which: R alkyl, cycloalkyl,

N \ < ¹²

R ' ¹ -' St ^R --Μ X ¹ ^ is selected from heterolakyl, cycloheteroalkyl, aryl, and derivatives thereof substituted inertly containing 1 to 30 atoms not containing hydrogen or a bivalent derivative thereof; T ¹ is a bivalent bridge-forming group of 1 to 41 atoms other than hydrogen, preferably 1 to 20 atoms other than hydrogen, and most preferably a silane or methylene group mono- or di-substituted with C1-20 hydrocarbyl ; θ R ¹² θ a C5-20 heteroaryl group containing Lewis base functionality, especially a substituted pyridin2-yl or pyridin-2-yl group or a divalent derivative thereof; M ¹ is a Group 4 metal, preferably hafnium; X ¹ is an anionic, neutral or di-anionic ligand group; x 'is a number from 0 to 5 indicating the number of such groups X ¹ ; and bonds, optional bonds and electron donor interactions are represented by lines, dashed lines and arrows respectively.

[0094] Preferred complexes are those in which the ligand formation results from the elimination of hydrogen from the amine group and optionally the loss of one or more additional groups, especially R ¹² . In addition, electron donation of the Lewis base functionality, preferably an electron pair, provides additional stability to the metal center. The preferred metal complexes correspond to the formula:

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70/130

in which Μ ¹ , X ¹ , x ', R ¹¹ and T ¹ are previously defined, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are hydrogen, halogen, or an alkyl, cycloalkyl, heteroalkyl, hetero-cycloalkyl, aryl group or silyl of up to 20 atoms not counting hydrogen, or adjacent R ¹³ , R ¹⁴ , R ¹⁵ or R ^{16 groups} can come together to form derivatives of fused rings, and bonds, optional bonds and electron donor interactions are represented by lines, lines dashes and arrows respectively.

[0095] More preferred examples of the previous metal complexes correspond to the formula:

Μ ¹ in which X ¹ and x 'are defined above, R ^13, R ^14,

R ¹⁵ and R ¹⁶ are defined above, preferably R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are hydrogen or C 1-4 alkyl, and C 20 aryl, most preferably naphthalenyl; each occurrence of R ^a is, independently, C1-4 alkyl, and a is 1-5, most preferably R ^a in the two positions ortho to nitrogen is isopropyl or terciobutyl; each occurrence of R ¹⁷ and R ¹⁸ is, independently, hydrogen, halogen or a C1-20 alkyl group or aryl, most preferably one of R ¹⁷ and R ¹⁸ is hydrogen and the other is a

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71/130 C6-20 aryl group / especially 2-isopropyl, phenyl or a fused polycyclic aryl group, most preferably an anthracenyl group, and connections, optional bonds and electron donor interactions are represented by lines, dashed lines and arrows respectively.

[0096] Very preferred metal complexes for use here correspond to the formula:

in which each occurrence of X ¹ is halide, N, N-dimethyl starch, or C 1-4 alkyl, and preferably each occurrence of X ¹ is methyl; each occurrence of R ^f is, independently, hydrogen, halogen, C1-20 alkyl / or C6-20 aryl / or two adjacent R ^f groups joining to form a ring, ef is 1-5; and each occurrence of R ^c is, independently, hydrogen, halogen, C1-20 alkyl / or C6-20 aryl / or two adjacent R ^c groups thus forming a ring, and c is 1-5.

[0097] Most preferred examples of complexes for use in accordance with the present invention are complexes of the following formulas:

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72/130

Q

in which R ^x is cycloalkyl or C1-4 alkyl, preferably methyl, isopropyl, terciobutyl or cyclohexyl; and each occurrence of X ¹ is halide, N, N-dimethyl starch, or C 1-4 alkyl, preferably methyl.

[0098] Examples of metal complexes usefully employed in accordance with the present invention include: dimethyl [N- (2, β-di (1-methyl-ethyl) phenyl) starch) (o-tolyl) (OC-naphthalene— 2- diyl (6-pyridin-2-diyl) methane] hafnium;

[N- (2, β-di (1-methyl-ethyl) phenyl) starch) di (N, N-dimethylamido) (o-tolyl) (a-naphthalene—

2-diyl (6-pyridin-2-diyl) methane] hafnium; [N- (2,6di (1-methyl-ethyl) phenyl) starch) pyridin-2-diyl) methane] hafnium dichloride; etii) phenyl) starch) (2-isopropyl pyridin-2-diyl) methane] hafnium;

(o-tolyl) (α-naphthalene — 2-diyl (6dimethyl [N- (2,6-di (1-methylphenyl) (α-naphthalene — 2-diyl (6di (N, N-dimethylamido)) [N- ( 2,6di (1-methyl-ethyl) phenyl) starch) (2-isopropyl phenyl) (a-naphthalene— 2-diyl (6-pyridin-2-diyl) methane] hafnium; [N- (2,6di dichloride (1-methyl-ethyl) phenyl) starch) (2-isopropyl phenyl) (a-naphthalene— 2-diyl (6-pyridin-2-diyl) methane] hafnium; dimethyl [N- (2,6-di (1methyl -ethyl) phenyl) starch) (phenanthren-5-yl) (oc-naphthalene — 2-diyl (6-pyridin-2-diyl) methane] hafnium; di (N, N-dimethyl starch) [N (2, 6-di ( 1-methyl-ethyl) phenyl) starch) (phenanthren-5-yl) (ocnaphthalene — 2-diyl (6-pyridin-2-diyl) methane] hafnium; and [N- (2,6-di (1-dichloride -methyl-ethyl) phenyl) starch) (phenanthren-5-yl) (ot—

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73/130 naphthalene — 2-diyl (6-pyridin-2-diyl) methane] hafnium.

[0099] In the reaction conditions used to prepare the metal complexes used in the present invention, the hydrogen of position 2 of the α-naphthalene group substituted in position 6 of the pyridin-2-yl group is subjected to elimination, thus forming exclusively metal complexes in which metal is covalently linked to both the resulting amide group and position 2 of the α-naphthalene group, as well as stabilized by coordination to the pyridinyl nitrogen atom through the electron pair of the nitrogen atom. [0100] Additional appropriate metal complexes of bases

multipurpose Lewis For use on here include compounds corresponding to the formula z ° v / ° ^X R ²⁰ 1 Gg where R ²⁰ is a group aromatic or one group aromatic inertly replaced containing out of 5 to 20 atoms not counting hydrogen, or a derivative multipurpose of same; T ³

it is a hydrocarbilene or silane group having from 1 to 20 atoms not counting hydrogen, or a polyvalent derivative thereof; M ³ is a Group 4 metal, preferably zirconium or hafnium; G is an anionic, neutral or di-anionic linking group; preferably a halide, hydrocarbyl or dihydrocarbyl amide group having up to 20 atoms not containing hydrogen; g is a number from 1 to 5 indicating the number of such groups G; and bonds, optional bonds and electron donor interactions are represented by lines, dashed lines and arrows respectively. Preferably, such complexes

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74/130 correspond to the formula:

in which T ³ is a bivalent bridge-forming group of 2 to 20 atoms not containing hydrogen, preferably a substituted or unsubstituted C3-6 alkylene group; and each occurrence of Ar ² is, independently, an arylene or arylene group substituted with alkyl or aryl of 6 to 20 atoms not containing hydrogen; M ³ is a Group 4 metal, preferably zirconium or hafnium; each occurrence of G is, independently, an anionic, neutral or dianionic linking group; g is a number from 1 to 5 indicating the number of such groups X; and electron donor interactions are represented by arrows.

[0101] Preferred examples of metal complexes of the previous formula include the following compounds:

where M ³ is Hf or Zr; Ar ⁴ is C6-20 aryl or derivatives thereof substituted inertly, especially 3,5di (isopropyl) phenyl, 3,5-di (isobutyl) phenyl, dibenzo-1H-pyrrol1-yl, or anthracen-5-yl, and each occurrence of T ⁴ comprises,

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75/130 independently, a C3-6 alkylene group, a C3-6 cycloalkylene group, or an inertly substituted derivative thereof; each occurrence of R ²¹ is, independently, hydrogen, halogen, hydrocarbyl, trihydrocarbyl silyl. or trihydrocarbil silyl hydrocarbyl of up to 50 atoms not counting hydrogen; and each occurrence of G is, independently, halogen or a hydrocarbyl or trihydrocarbyl silyl group of up to 20 atoms not counting hydrogen, or 2 G groups together are a divalent derivative of the previous hydrocarbyl or trihydrocarbyl silyl groups. Especially preferred are the compounds of the formula:

R ^2!

in which Ar ⁴ is 3,5-di (isopropyl) phenyl, 3,5-di (isobutyl) phenyl, dibenzo-1H-pyrrol-l-yl, or anthracen-5-yl, R ²¹ is hydrogen, halogen, or C1-4 alkyl, especially methyl, T ⁴ is propane-1,3-diyl or butane-1,4-diyl, and G is chlorine, methyl or benzyl.

[0102] A highly preferred metal complex of the previous formula is:

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[0103] The previous multipurpose Lewis base complexes are conveniently prepared by standard metallization and ligand exchange procedures involving a Group 4 metal source and the neutral polyfunctional ligand source. In addition, the complexes can also be prepared by means of an amide elimination and hydrocarbilization process starting from the corresponding Group 4 metal tetra-amide and a hydrocarbilizing agent, such as trimethyl aluminum. Other techniques can also be used. These complexes are known from the disclosures in , among others, US patents ^Nos 6,320,005 s, 6,103,657, WO 02/38628, WO 03/40195, and WO 04-0220050.

[0104] Additional metal compounds for use here include metal derivatives of Groups 4-10 corresponding to the formula:

M ² X ² x ·· in which M ² is a metal in Groups 4-10 of the Periodic Table of

Elements, preferably Group 4, Ni (II) or

Pd (II), most preferably zirconium; T ² is a group

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77/130 containing nitrogen, oxygen or phosphorus; X ² is halogen, hydrocarbyl, or hydrocarbiloxy; t is one or two; x is a number selected to provide load balancing; and T ² and N are linked by a bridge-forming ligand.

[0105] Such catalysts were previously disclosed in J. Am. Chem. Soc., 118, 267-268 (1996), J. Am. Chem. Soc., 117, 6414-6415 (1995), and in Organometallics, 16, 1514-1516 (1997), among other disclosures.

[0106] Preferred examples of the previous metal complexes are diimine and aromatic dioxyimine complexes of Group 4 metals, especially zirconium, corresponding to the formula:

in which: Μ ² , X ² and T ² are defined previously; each occurrence of R ^d is, independently, hydrogen, halogen, or R ^e ; and each occurrence of R ^e is independently C1-20 hydrocarbyl or a heteroatom-substituted derivative thereof, especially F, N, S or P, more preferably C1-10 hydrocarbyl or a derivative of the same substituted by F or N , most preferably alkyl, dialkylamino alkyl, pyrrolyl, piperidinyl, perfluorophenyl, cycloalkyl, (poly) alkyl aryl, or aralkyl.

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78/130 [0107] The most preferred examples of the previous metal complexes are the zirconium dioxyimine complexes corresponding to the formula:

(H3Q3

C (CH ₃ ) ₃ in which: X ² is defined above, preferably C 1-10 hydrocarbyl, most preferably methyl or benzyl; and R ^e 'is methyl, isopropyl, terciobutyl, cyclopentyl, cyclohexyl, 2-methyl-cyclohexyl, 2,4dimethyl-cyclohexyl, 2-pyrrolyl, N-methyl-2-pyrrolyl, 2piperidinyl, N-methyl -2-piperidinyl, benzyl, o-tolyl, 2,6-dimethyl-phenyl, perfluorophenyl, 2,6-di (isopropyl) phenyl, or 2,4,6-trimethyl-phenyl.

[0108] The foregoing complexes also include certain phosphinimine complexes which are disclosed in EP-A-890581. These complexes correspond to the formula:

[(R ^f ) 3-P = N] fM (K ² ) (R ^f ) 3-f in which R ^f is a monovalent linker or two R ^f groups together

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79/130 are a divalent linker, preferably R ^f is hydrogen or C1-4 alkyl; M is a Group 4 metal; K ² is a group containing delocalized π electrons through which K ² binds to dito, said K ² group containing up to 50 atoms not containing hydrogen atoms; ef is 1 or 2.

[0109] Catalysts having high comonomer incorporation properties are also known to reincorporate long-chain defines prepared at the resulting site incidentally during polymerization through β hydride elimination and growing polymer chain termination, or other process. The concentration of such long chain settings is particularly improved by using continuous solution polymerization conditions at high conversions, especially conversions of ethylene of 95 percent or greater, more preferably in conversions of ethylene of 97 percent or greater. Under such conditions a small but detectable amount of vinyl group-terminated polymer can be reincorporated into a growing polymeric chain, resulting in the formation of long chain branches, that is, branches of a longer carbon length than would result from another comonomer added deliberately. In addition, such chains reflect the presence of other comonomers present in the reaction mixture. That is, the chains may also include short- or long-chain branching, depending on the comonomer composition of the reaction mixture. However, the presence of MSA or CSA during polymerization can seriously limit the incidence of long chain branching since the vast majority of polymer chains become linked to an MSA or CSA species and are prevented from undergoing β hydride elimination.

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Co-catalysts [0110] Each of the metal complexes (also referred to here, in order to allow exchange or substitution, as procatalysts) can be activated to form the active catalyst composition in combination with a co-catalyst, preferably a forming co-catalyst of cation, a strong Lewis acid, or a combination thereof.

[0111] Cation-forming co-catalysts include those previously known in the art for use with Group 4 olefinic metal polymerization complexes. Examples include neutral Lewis acids, such as Group 13 compounds substituted with C1-30 hydrocarbyl, especially compounds of tri (hydrocarbyl) aluminum or tri (hydrocarbyl) boron or halogenated derivatives thereof (including perhalogenated), having from 1 to 10 carbon atoms in each hydrocarbyl or halogenated hydrocarbyl group, more especially tri (aryl) compounds perfluorinated boron, and most especially tris (pentafluoro phenyl) borane; non-polymeric, compatible, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions), especially the use of compatible non-coordinating anions, ammonium, phosphonium, oxonium, silicon or sulfonium salts or ferrocene salts , lead or silver from compatible non-coordinating anions; and combinations of prior and technical cation-forming co-catalysts. The activating techniques and previous activating co-catalysts were previously taught with respect to the different metal complexes for olefinic polymerizations in the following references: EPA-277.003, US-A-5.153.157, US-A-5.064.802, US-A- 5,321,106,

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US-A-5,721,185, US-A-5,350,723, US-A-5,425,872, US-A5,625,087, US-A-5,883,204, US-A-5,919,983, US-A- 5,783,512, WO 99/15534, and WO 99/42467.

[0112] Neutral Lewis acid combinations can be used as activating co-catalysts, especially the combination of a trialkyl aluminum compound having 1 to 4 carbon atoms in each alkyl group and a halogenated tri (hydrocarbyl) compound having from 1 to 20 carbon atoms in each hydrocarbyl group, especially tris (pentafluoro phenyl) borane, additional combinations of such mixtures of neutral Lewis acids with a polymeric or oligomeric aluminoxane, and combinations of a single neutral Lewis acid. The preferred molar ratios of metal complex: tris (pentafluoro phenyl) borane: aluminoxane are from 1: 1: 1 to 1: 5: 20, more preferably from 1: 1: 1.5 to 1: 5: 10. [0113] In an embodiment of the present invention, the appropriate ion-forming compounds useful as cocatalysts comprise a cation which is a Brõnsted acid capable of donating a proton, and a non-coordinating A ”anion compatible. As used here, the term non-coordinating means an anion or substance that either does not coordinate with the precursor complex containing Group 4 metal and the catalytic derivative that derives from it, or that is only weakly coordinated with such complexes and thus remains unstable enough to be displaced by a neutral Lewis base. A non-coordinating anion refers specifically to an anion that when it functions as a load-balancing anion in a cationic metal complex does not transfer an anionic substituent or fragment thereof to said cation, thus forming neutral complexes. Anions

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82/130 compatible are anions that do not degrade to neutrality when the complex initially formed decomposes and do not interfere with the desired subsequent polymerization or other uses of the complex.

[0114] Preferred anions are those containing a single coordination complex comprising a metal or metalloid nucleus carrying a charge, and which are capable of balancing the charge of the active catalytic species (the metallic cation) that can be formed when the two components combine . Likewise, said anion must be sufficiently unstable to be displaced by olefinic, diolefinic and acetylenically unsaturated compounds or by other neutral Lewis bases such as ethers or nitriles. Suitable metals include, but are not limited to, aluminum, gold and platinum. Suitable metalloids include, but are not limited to, boron, phosphorus, and silicon. anion-containing compounds comprising coordination complexes containing a single metal or metalloid atom are certainly well known and many, particularly such compounds containing a single boron atom in the anionic portion, are commercially obtainable.

[0115] Preferably such co-catalysts can be represented by the following general formula:

(L * -H) _g ⁺ (A) ^g “in which L * is a neutral Lewis base; (L * -H) ⁺ is an L * conjugated Brõnsted acid; The ⁹ ”is a non-coordinating compatible anion having a g- charge; eg is an integer from 1 to 3.

[0116] More preferably, A ⁹ "corresponds to the formula [MiQ ₄ ]", in which Mi is boron or aluminum in the +3 formal oxidation state; and each occurrence of Q is independently

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83/130 selected from hydride, dialkyl starch, halide, hydrocarbyl, hydrocarbyloxide, hydrocarbyl substituted by halogen, hydrocarbyloxy substituted by halogen, and hydrocarbyl radicals substituted by halogen (including perhalogenated hydrocarbyl radicals, perhalogenated hydrocarbyloxy and perhydrated hydrocarbyl radicals halogenated), said Q having up to 20 carbon atoms with the proviso that in no more than one occurrence Q is halide. Examples of Q hydrocarbiloxide groups are disclosed in US-A-5,296,433.

[0117] In a more preferred embodiment, d is one, that is, the counterion has only one negative charge and is A ”. Activating cocatalysts comprising boron which are particularly useful in the preparation of catalysts of this invention can be represented by the following general formula: (L * -H) ⁺ (BQ ₄ ) “in which L * is defined above; B is boron in an oxidation state of 3; and Q is a hydrocarbyl, hydrocarbiloxy, fluorinated hydrocarbyl, fluorinated hydrocarbyl, or fluorinated hydrocarbyl group of up to 20 non-hydrogen atoms, with the proviso that in no more than one condition Q is hydrocarbyl.

[0118] Preferred Lewis base salts are ammonium salts, more preferably trialkyl ammonium salts containing one or more C12-40 alkyl groups · Most preferably, each occurrence of Q is a fluorinated aryl group, especially a pentafluorophenyl group .

[0119] Illustrative, but not limiting, examples of boron compounds that can be used as an activating co-catalyst in the preparation of the improved catalysts of this invention are the tri-substituted ammonium salts such as:

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84/130 tetrakis (pentafluoro tetrakis (pentafluoro

phenyl) borate of trimethyl ammonium, phenyl) borate from trietil ammonium, phenyl) borate tri (propyl) ammonium, phenyl) borate in tri (n-butyl) ammonium, phenyl) borate tri (sec-butyl) ammonium, phenyl) borate in Ν, Ν-dimethyl anilinium,

n-butyl tris (pentafluoro phenyl) N, N-dimethyl anilinium borate, benzyl tris (pentafluoro phenyl) N, N-dimethyl anilinium borate, tetrakis (4- (terciobutyl dimethyl silyl) -2,3,5,6tetrafluoro phenyl ) borate tetrakis (4- (iso-dimethyl anilinium, silyl) -2,3,5,6-tetrafluoro phenyl) bor, Ν-dimethyl anilinium, pentafluoro phenoxy tris (pentafluoro phenyl)

N, N-dimethyl anilinium, etra tetrakis (pentafluoro phenyl) borate, Ν-diethyl anilinium, tetrakis (pentafluoro phenyl) dimethyl ammonium borate, tetrakis (pentafluoro phenyl) methyl di octadecyl borate (octadecyl) ammonium; dialkyl ammonium salts such as: tetrakis (pentafluoro phenyl) di (isopropyl) ammonium borate, tetrakis (pentafluoro phenyl) methyl octadecyl ammonium borate, and tetrakis (pentafluoro phenyl) di (octadecyl) ammonium borate; tri-substituted phosphonium salts such as: tetrakis (pentafluoro phenyl) triphenyl phosphonium borate, tetrakis (pentafluoro phenyl) methyl di (octadecyl) phosphonium borate, and tetrakis (pentafluoro phenyl) tri (2,6-dimethyl phenyl) borate phosphonium; disubstituted oxonium salts such as: tetrakis (pentafluoro phenyl) diphenyl oxonium borate, tetrakis (pentafluoro phenyl) di (otolyl) oxonium borate, and tetrakis (pentafluoro phenyl) di (octadecyl) oxide borate; di-substituted sulfonium salts such as: tetrakis (pentafluoro phenyl) di borate (oPetition 870170056094, from 08/04/2017, page 91/141

85/130 tolyl) sulfonium, and tetrakis (pentafluoro phenyl) methyl octadecyl sulfonium borate.

[0120] Preferred (L * -H) ⁺ cations are methyl di (octadecyl) ammonium cations, dimethyl octadecyl ammonium cations, and ammonium cations derived from mixtures of trialkylamines containing one or 2 C14-18 alkyl groups · [0121] Other The appropriate ion-forming activating co-catalyst comprises a salt of a cationic oxidizing agent and a compatible non-coordinating anion represented by the formula:

(Ox ^{h +} ) g (A ^g -) h in which: Ox ^{h +} is a cationic oxidizing agent having a charge of h +; h is an integer from 1 to 3; and A ⁹ ”eg are defined previously.

[0122] Examples of cationic oxidizing agents include: ferrocene, ferrocenium substituted by hydrocarbyl, Ag ⁺ or Pb ⁺² . Preferred embodiments of A ⁹ ”are those anions previously defined with respect to activating co-catalysts containing Brõnsted acid, especially tetrakis (pentafluoro phenyl) borate.

[0123] Another appropriate ion-forming activating co-catalyst comprises a compound that is a carbenium ion salt and a compatible non-coordinating anion represented by the formula:

[C] ⁺ A in which: [C] ⁺ is a C1-20 carbenium ion; and A ”is a non-coordinating compatible anion having a charge of -1. A preferred carbenium ion is the trityl cation, which is triphenyl methyl.

[0124] An additional appropriate ion-forming activating co-catalyst comprises a compound which is a salt of

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86/130 silicon ion and a compatible non-coordinating anion represented by the formula:

(qSsd + ana which; Q ¹ is Ci-io hydrocarbyl; and A ”is defined previously.

[0125] Preferred silyl salt activating co-catalysts are tetrakis (pentafluoro phenyl) trimethyl silyl borate, tetrakis (pentafluoro phenyl) triethyl silyl borate and adducts thereof replaced by ether. In general, silyl salts were previously disclosed in J. Chem. Soc. Chem. Comm., 1993, 383-384, as well as in Lambert, J.B. et al., Organometallics, 1994, 13, 2430-2443. The use of the above silyl salts as activating co-catalysts for addition polymerization catalysts is disclosed in US-A-5,625,087.

[0126] Certain complexes of alcohols, mercaptan, silanols, and oximes with tris (pentafluoro phenyl) borane are also effective catalytic activators and can be used in accordance with the present invention. Such co-catalysts are disclosed in US-A-5,296,433.

[0127] Activating co-catalysts suitable for use here also include polymeric or oligomeric aluminoxanes, especially methyl aluminoxane (MAO), methyl aluminoxane modified with triisobutyl aluminum (MMAO), or isobutyl aluminoxane; Lewis acid-modified aluminoxanes, especially aluminoxanes modified by perhalogenated tri (hydrocarbyl) aluminum or perhalogenated tri (hydrocarbyl) boron, having from 1 to 10 carbon atoms in each halogenated hydrocarbyl or hydrocarbyl group, and very especially aluminoxanes

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87/130 modified by tris (pentafluoro phenyl) borane. Previously-disclosed is such co-catalysts in US Patent ^Nos 6,214,760 s, 6,160,146, 6,140,521, and 6,696,379.

[0128] A class of cocatalysts comprising non - coordinating anions generically referred to as expanded anions, further disclosed in US Patent ^Nos 6,395,671, may be suitably employed to activate the metal complexes of the present invention for olefin polymerization. Generally, these co-catalysts (illustrated by those having anions imidazolid, substituted imidazolid, imidazolinide, substituted imidazolinide, benzimidazolid, or being represented as if substituted benzimidazolid) can follow:

Q ³ Q ³

in which: A * ⁺ is a cation, especially a proton-containing cation, and preferably is a trihydrocarbyl ammonium cation containing one or two Cio-40 alkyl groups, especially a methyl di (C14-20 alkyl) ammonium cation; each occurrence of Q ³ is independently hydrogen or a halogen, hydrocarbyl, halocarbyl, halogenated hydrocarbyl, hydrocarbyl, or silyl (including mono, di and tri (hydrocarbyl) silyl) of up to 30 atoms not containing hydrogen, preferably alkyl of C1-20; and Q ² is tris (pentafluoro phenyl) borane or tris (pentafluoro phenyl) aluminane.

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88/130 [0129] Examples of these catalytic activators include tri (hydrocarbyl) ammonium salts, especially methyl di (C14-20 alkyl) ammonium salts of: bis (tris (pentafluoro phenyl) borane) imidazolid, bis (tris (pentafluoro phenyl) borane) 2-undecyl imidazolid, bis (tris (pentafluoro phenyl) borane) -2heptadecyl imidazolid, bis (tris (pentafluoro phenyl) borane) 4.5- bis (undecyl) imidazolid, bis (tris (pentafluoro phenyl) borane) -4 , 5-bis (heptadecyl) imidazolid, bis (tris (pentafluoro phenyl) borane) imidazolinide, bis (tris (pentafluoro phenyl) borane) -2-undecyl imidazolinide, bis (tris (pentafluoro phenyl) borane) -2- heptadecyl imidazolinide, bis (tris (pentafluoro phenyl) borane) -4,5bis (undecyl) imidazolinide, bis (tris (pentafluoro phenyl) borane) -4,5-bis (heptadecyl) imidazolinide, bis (tris (pentafluoro phenyl) alumano) imidazolid, bis (tris (pentafluoro phenyl) alumino) -2-undecyl imidazolid, bis (tris (pentafluoro phenyl) alumano) -2-heptadecyl imidazolid, bis (tris (pentafluoro phenyl) alumano) -4,5bis (undecil) imidazolid, bis ( tris (pentafluoro phenyl) alumino) 4.5- bis (heptadecyl) imidazolid, bis (tris (pentafluoro phenyl) alumano) imidazolinide, bis (tris (pentafluoro phenyl) alumano) -2-undecyl imidazolinide, bis (tris (pentafluoro phenyl) alumina) -2- heptadecyl imidazolinide, bis (tris (pentafluoro phenyl) alumino) -4,5bis (undecyl) imidazolinide, bis (tris (pentafluoro phenyl) alumano) -4,5-bis (heptadecyl) imidazolinide, bis (tris (pentafluoro phenyl) ) alumina) -5,6-dimethyl benzimidazolid, and bis (tris (pentafluoro phenyl) alumina) -5.6 bis (undecyl) benzimidazolid.

[0130] Other activators include those described in

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89/130 PCT publication WO 98/07515 such as tris (2,2 ', 2-ninth fluoro phenyl) fluoro aluminate. Combinations of activators are also considered by the invention, for example, alumoxanes and ionizing activators in combinations, see for example EP- A -0 573 120, WO 94/07928 and PCT publications WO 95/14044, and US Patent Nos 5,153,157 ^2s and 5,453,410. WO 98/09996 describes catalytic activating compounds with perchlorates, periodates and iodates, including their hydrates. WO 99/18135 describes the use of organic aluminum boron activators. WO 03/10171 discloses catalyst activators that are adducts of Brõnsted acids with Lewis acids. Other activators or methods for activating a catalyst compound are described, for example, in US Patent No 5,849,852 ^2s, 5,859,653, 5,869,723, EP-A-615 981, and PCT publication WO 98/32775. All previous catalyst activators as well as any other known activator for transition metal complex catalysts can be used alone or in combination according to the present invention, however, for better results, aluminoxane-containing co-catalysts are avoided.

The catalyst / co-catalyst molar ratio employed ranges preferably from 1: 10,000 to 100: 1, more preferably from 1: 5000 to 10: 1, most preferably from 1: 1000 to 1: 1. Aluminoxane, when used as an activating co-catalyst, is used in large quantities, usually at least 100 times the amount of metal complex on a molar basis. Tris (pentafluoro phenyl) borane, where used as an activating co-catalyst, is used in a molar ratio for the metal complex of 0.5: 1 to 10: 1, more preferably 1: 1 to 6: 1, most preferably of

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1: 1 to 5: 1. The remaining activating co-catalysts are generally employed in an amount approximately equimolar with the metal complex.

[0132] During polymerization, the reaction mixture is contacted with the activated catalytic composition according to any appropriate polymerization conditions. Desirably, the process is characterized by the use of high pressures and temperatures. If desired, hydrogen can be used as a chain transfer agent to control molecular weight according to known techniques. In other similar polymerizations, it is very desirable that the monomers and solvents employed are of sufficiently high purity so that catalyst deactivation or premature chain termination does not occur. Any suitable technique for purifying monomer can be employed such as devolatilization under reduced pressure, contacting with molecular sieves or high surface area alumina, or a combination of the previous processes.

[0133] In the present invention it is possible to use supports, especially in polymerizations in mud or gas phase. Suitable supports include solid particulate metal oxides with a high surface area, metalloid oxides, or mixtures thereof (referred to to allow exchange or replacement as inorganic oxides). Examples include: talc, silica, alumina, magnesia, titania, zirconia, Sn ₂ O3, aluminum silicates, boron silicates, clays, and mixtures thereof. Preferably, the appropriate substrates have a surface area determined by nitrogen porosimetry using the 10 to BET method

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1000 m ² / g, and preferably from 100 to 600 m ² / g. Typically, the average particle size is 0.1 to 500 µm, preferably 1 to 200 μιη, more preferably 10 to 100 μιη.

[0134] In an embodiment of the invention the present catalytic composition and the optional support can be sprayed dry or otherwise recovered in a particulate, solid form to provide a composition for rapid transport and handling. Appropriate methods of spraying a liquid-containing slurry to dry are well known in the art and usefully employed here. Preferred techniques for spraying following catalytic compositions for use here are described in US-A-5,648,310 and US-A-5,672,669.

[0135] Desirably, polymerization is carried out as a continuous polymerization, preferably a continuous solution polymerization, in which the catalyst components, monomers, and optionally solvents, adjuvants, cleaners, and polymerization aids are supplied continuously to one or more more reactors or zones and the polymeric product removed from there. Within the limits of the scope of the terms continuously and continuously used in this context, are those processes in which there are intermittent additions of reagents and removal of products at small regular or irregular intervals, so that, over time, the overall process is substantially continuous . Although the multi-center exchange agent and chain exchange agent (if used) can be added at any point during polymerization including in the first reactor or zone, at the outlet or just before the outlet of the first reactor, between the first reactor or zone and any reactor or zone

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92/130 thereafter, or even exclusively in the second reactor or zone, if present, preferably both are added in the initial stages of polymerization. IF there is any difference in monomers, temperatures, pressures or other polymerization condition within a reactor or between two or more reactors or zones connected in series, within the same molecule of the polymers of the invention, polymeric segments of different composition will form such as comonomer content, crystallinity, density, tactility, regularity, or other physical or chemical difference. In such an event, the size of each segment or block is determined by the polymeric reaction conditions, and preferably it is a most likely distribution of polymer sizes.

[0136] If multiple reactors are used, each of them can be operated independently under conditions of high pressure polymerization, in solution, in mud, or in gas phase. In a multiple zone polymerization, all zones operate in the same type of polymerization, such as in solution, slurry or gaseous phase, but, optionally, under different process conditions. For a solution polymerization process, it is desirable to employ homogeneous dispersions of the catalyst components in a liquid diluent in which the polymer is soluble under the employed polymerization conditions. Such a process is disclosed using an extremely fine silica or similar dispersing agent to produce such a homogeneous catalyst dispersion in which normally either the metal complex or the co-catalyst is only slightly soluble in US-A-5,783,512. A high pressure process is carried out at temperatures from 100 ° C to 400 ° C and

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93/130 at pressures above 50 MPa (500 bar). Typically, a sludge process uses an inert hydrocarbon diluent and temperatures from 0 ° C to a temperature just below the temperature at which the resulting polymer becomes substantially soluble in the inert polarization medium. In a sludge polymerization, preferred temperatures are 30 ° C, preferably 60 ° C to 115 ° C, preferably up to 100 ° C, depending on the polymer being prepared. Typically pressures range from atmospheric pressure (100 kPa) to 3.4 MPa (500 psi).

[0137] Preferably, continuous or substantially continuous polymerization conditions are employed in all of the above processes. The use of such polymerization conditions, especially in continuous solution polymerization processes, allows the use of high reactor temperatures which results in the economical production of the present block copolymers in high yields and efficiencies.

[0138] The catalyst can be prepared as a homogeneous composition by adding the metal complex or multiple indispensable complexes in a solvent in which the polymerization will be carried out or in a diluent compatible with the final reagent mixture. The desired co-catalyst or activator and, optionally, an exchange agent can be combined with the catalytic composition before, simultaneously or after combining the catalyst with the monomers to be polymerized and any additional reaction diluents. Desirably the MSA is added at the same time.

[0139] Individual ingredients as well as any active catalytic compositions must always be protected from

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94/130 oxygen, moisture and other catalytic poisons. Therefore, the components of catalyst, multi-center exchange agent and activated catalysts should be prepared and stored in an atmosphere free of moisture oxygen, preferably in a dry inert gas such as nitrogen.

[0140] Without limiting the scope of the invention in any way, a means of carrying out such a polymerization process is as follows. In one or more loop or well reactor reactors operating under solution polymerization conditions, the monomers to be polymerized together with any solvent or diluent are continuously introduced into a part of the reactor. The reactor contains a relatively homogeneous liquid phase composed substantially of monomers together with any solvent or diluent and dissolved polymer. Preferred solvents include C4-10 hydrocarbons or mixtures thereof, especially alkanes such as hexane or mixtures of alkanes, as well as one or more of the monomers employed in the polymerization. Examples of suitable loop reactors and a variety of operating conditions suitable for use with them, including multiple loop reactors, operating in series, are found at USP's 5,977,251, 6,319,989 and 6,683,149.

[0141] The catalyst together with the co-catalyst and the multi-center exchange agent are continuously or intermittently introduced into the liquid phase of the reactor or any recycled portion thereof in a minimum of one location. The reactor pressure and temperature can be controlled by adjusting the solvent / monomer ratio, the catalyst addition rate, as well as by using cooling or heating coils, liners or both. The rate of

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95/130 polymerization by the rate of addition of catalyst. The content of a given monomer in the product polymer is influenced by the ratio of monomers in the reactor, which is controlled by manipulating the respective feed rates of these components to the reactor. Optionally, the molecular weight of the product polymer is controlled by controlling other polymerization variables such as temperature, monomer concentration, or by the multi-center exchange agent mentioned above, or a chain terminating agent such as hydrogen, as is well known in the technique.

[0142]

In an embodiment of the invention, a second reactor is connected to the reactor discharge, optionally by means of a conduit or other transfer medium, such that the reaction mixture prepared in the first reactor is discharged into the second reactor without substantial termination of polymeric growth. Between the first and the second reactor, a difference can be established in at least one process condition. Preferably for use in forming a copolymer of two or more monomers, the difference is the presence or absence of one or more comonomers or a difference in the comonomer concentration. Additional reactors can also be provided, each arranged similarly to the second reactor in the series. The polymerization can further be terminated by contacting the reactor effluent with a catalyst inhibiting agent such as water, steam or alcohol or with a coupling agent if a coupled reaction product is desired.

[0143] The resulting polymer product is recovered by vaporizing volatile components of the reaction mixture such as residual monomer or diluent under reduced pressure, and if

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96/130 necessary, perform additional devolatilization in equipment such as a devolatilizer extruder. In a continuous process the average residence time of the catalyst and polymer in the reactor is generally from 5 minutes to 8 hours, and preferably from 10 minutes to 6 hours.

[0144] Alternatively, the previous polymerization can be carried out in a flow reactor optionally capped with a monomer, catalyst, multi-center exchange agent, temperature or other gradient established between different zones or regions thereof, optionally still accompanied by separate addition of catalysts and / or chain exchange agent, and operating under adiabatic or non-adiabatic polymerization conditions.

[0145] The catalytic composition can also be prepared and used as a heterogeneous catalyst by adsorbing the essential components in an inert organic or inorganic particulate solid, previously disclosed. In a preferred embodiment, a heterogeneous catalyst is prepared co-precipitating the metal complex and the reaction product of an inert inorganic compound and an activator containing active hydrogen, especially the reaction product of a tri (C1-4 alkyl) aluminum compound with an ammonium salt of hydroxy aryl tris (pentafluoro phenyl) borate, such as an ammonium salt of (4-hydroxy-3,5-ditherciobutyl phenyl) tris (pentafluoro phenyl) borate. When prepared in heterogeneous form or in support, the catalytic composition can be used in a polymerization in mud or gas phase. As a practical limitation, sludge polymerization occurs in liquid diluents in which the polymer product is substantially insoluble. Preferably, the diluent for

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97/130 sludge polymerization is one or more hydrocarbons with less than 5 carbon atoms. If desired, saturated hydrocarbons such as ethane, propane or butane can be used in whole or in part as the diluent. In solution polymerization the α-olefin comonomer or a mixture of different α-olefin monomers can be used totally or partially as the diluent. Most preferably at least most of the diluent comprises the monomer or monomers of α-olefins to be polymerized.

[0146] Preferably for use in gas phase polymerization processes, the support material and the resulting catalyst have an average particle diameter of 20 to 200 μτη, more preferably from 30 mg to 150 gm, and most preferably from 50 gm to 100 gm. Preferably for use in sludge polymerization processes, the support material has an average particle diameter from 1 gm to 200 gm, more preferably from 5 mg to 100 gm, and most preferably from 10 gm to 80 gm.

[0147] The gas phase polymerization processes, suitable for use here, are substantially similar to the known processes used commercially on a large scale for the manufacture of polypropylene, ethylene / a-olefin copolymers, and other olefinic polymers. The gas phase process employed can be, for example, of the type that employs a mechanically agitated bed or a fluidized gas bed as the polymerization reaction zone. The process is preferred as the polymerization reaction is carried out in a vertical cylindrical polymerization reactor containing a fluidized bed consisting of supported polymer particles

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98/130 or suspended above a perforated plate or fluidization grid, by a flow of fluidizing gas.

[0148] The gas used to fluidize the bed comprises the monomer or monomers to be polymerized, and also serves as a heat exchanger medium to remove the reaction heat from the bed. Hot gases emerge from the top of the reactor, usually via a tranquilizer zone, also known as a speed reduction zone, having a diameter larger than that of the fluidized bed and fine particles entrained in the gas stream have an opportunity, by gravity , return to bed. It can also be advantageous to use a cyclone to remove ultrafine particles from the hot gas stream. The gas is then normally recycled to the bed by means of a blower or compressor and one or more heat exchangers to extract the gas from the polymerization heat.

[0149] A preferred method of cooling the bed, in addition to the cooling provided by the cooled recycle gas, is to feed a volatile liquid into the bed to provide an evaporative cooling effect, often referred to as condenser mode operation. The volatile liquid employed in this case can be, for example, a volatile inert liquid, for example, a saturated hydrocarbon having from 3 to 8, preferably from 4 to 6 carbon atoms. In the event that the monomer or comonomer itself is a volatile liquid, or can be condensed to provide such a liquid, it can be properly fed into the bed to provide an evaporative cooling effect. The volatile liquid evaporates in the hot fluidized bed to form gas that mixes with the fluidizing gas. If the volatile liquid is a monomer or

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99/130 comonomer, it will undergo some polymerization in the bed. The evaporated liquid then emerges from the reactor as part of the hot recycle gas, and enters the compression / heat exchange part of the recycle loop. The recycle gas is cooled in the heat exchanger and, if the temperature at which the gas is cooled is below the dew point, the liquid will precipitate from the gas. This liquid is desirably recycled continuously to the fluidized bed. It is possible to recycle the precipitated liquid into the bed as liquid droplets carried in the recycling gas stream. This type of process is described, for example, in EP-89691, U.S. 4,543,399, WO 94/25495 and U.S. 5,352,749. A particularly preferred method of recycling the liquid into the bed is to separate the liquid from the recycle gas stream and reinject this liquid directly into the bed, preferably using a method that generates fine droplets of the liquid within the bed. This type of process is described in WO 94/28032.

[0150] The polymerization reaction that occurs in the gaseous fluidized bed is catalyzed by the continuous or semi-continuous addition of the previously disclosed catalytic composition. The catalytic composition can be subjected to a prepolymerization step, for example, polymerizing a small amount of olefinic monomer in an inert liquid diluent, to provide a catalytic composite comprising supported catalyst particles embedded in olefinic polymer particles as well.

[0151] The polymer is produced directly in the fluidized bed by polymerization of the monomer or mixture of monomers on the fluidized particles of composition

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100/130 catalytic, supported catalytic composition or pre-polymerized catalytic composition within the bed. The initiation of the polymerization reaction is achieved by using a bed of preformed polymer particles, which are preferably similar to those of the desired polymer, and conditioning the bed by drying with nitrogen or inert gas before introducing the catalytic composition, monomers and any other gases that you want to have in the recycle gas stream, such as a diluent gas, hydrogen chain transfer agent, or an inert condensable gas when operating and phase condensation mode. When desired, the polymer produced is discharged continuously or semi-continuously from the fluidized bed.

[0152] The gas phase processes most suitable for the practice of this invention are continuous processes that provide the continuous supply of reagents to the reaction zone of the reactor and the removal of products from the reaction zone of the reactor, thus providing a stationary environment in macro scale in the reaction zone of the reactor. The products are quickly recovered by exposure to reduced pressure and optionally high temperatures (devolatilization) according to known techniques. Typically, the fluidized bed of the process is operated in gas phase at temperatures greater than 50 ° C, preferably from 60 ° C to 110 ° C, more preferably from 70 ° C to 110 ° C.

[0153] I Gas phase processes appropriate that are adaptable for use in the process of this invention are disclosed in US patents n ² s 4,588,790, 4,543,399, 5,352,749, 5,436,304, 5,405,922, 5,462,999, 5,461,123, 5,453,471, 5,032,562, 5,028,670, 5,473,028, 5,106,804,

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101/130

5,556,238, 5,541,270, 5,608,019, and 5,616,661.

[0154] As mentioned earlier, functionalized polymer derivatives are also included in the invention. Examples include metallized polymers in which the metal is the rest of the catalyst or chain exchange agent employed, as well as derivatives thereof. Since a substantial fraction of the polymeric product leaving the reactor ends with the multi-center exchange agent, additional functionalization is relatively easy. The metallized polymer species can be used in well-known chemical reactions such as those suitable for other alkyl aluminum, alkyl gallium, alkyl zinc, or Group 1 alkyl compounds to form products terminated by amine, hydroxy, epoxy, silane, vinyls and terminated by other features. Examples of appropriate reaction techniques that are adaptable for use here are described in Negishi, Organometallics in Organic Synthesis, volumes 1 and 2, (1980), and other standard texts on organometallic and organic synthesis.

Polymeric products [0155] Using the present process, new polymeric compositions, including pseudoblocks copolymers of one or more olefinic monomers having the present bimodal molecular weight distribution, are rapidly prepared. Preferred polymers comprise in polymerized form at least one monomer selected from the group consisting of ethylene, propylene and 4-methyl-1-pentene. Most desirably, polymers are interpolymers comprising in polymerized form ethylene, propylene or 4-methyl-1-pentene and at least one α-olefin comonomer of

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C2-20, θ optionally one or more additional copolymerizable comonomers. The appropriate comonomers are selected from diolefins, cyclic olefins, and cyclic diolefins, halogenated vinyl compounds, and aromatic vinylidene compounds. Preferred polymers are ethylene interpolymers with 1-butene, 1-hexene or 1-octene. Desirably, the polymeric compositions of the invention have an ethylene content of 1 to 99 percent, a diene content of 0 to 10 percent, and a C3-8 styrene and / or α-olefin content of 99 to 1 percent based on the total weight of the polymer. Most preferably, the polymers of the invention have a weight average molecular weight (Mw) of 10,000 to 2,500,000.

[0156] The polymers of the invention can have a melting index, I ₂ , of 0.01 to 2000 g / 10 minutes, preferably 0.01 to 1000 g / 10 minutes, more preferably 0.01 to 500 g / 10 minutes, and especially from 0.01 to 100 g / 10 minutes.

Desirably, the invented polymers can have molecular weights, Mw, of

1,000 g / mol to 5,000,000 g / mol, preferably 1000 g / mol to 1,000,000 g / mol, more preferably 1000 g / mol

500,000 g / mol, especially from 1000 g / mol to 300,000 g / mol. The density of the invented polymers can be from 0.80 to 0.99 g / cm ³ and preferably, for polymers containing ethylene, from 0.85 g / cm ³ to 0.97 g / cm ³ .

[0157] The polymers of the invention can be differentiated from conventional random copolymers, physical mixtures of polymers, and from block copolymers prepared via the addition of sequential monomer, fluxionary catalysts, or by cationic or live anionic polymerization techniques, due to weight distribution single molecular mentioned

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103/130 previously. If present, the regions or separate blocks within different polymers depending on uniformity are relatively uniform, of reactor conditions, and chemically of each other. That is, the comonomer distribution, tacticity, or other property of segments within the polymer are relatively uniform within the same block or segment. However, the average block length is not a narrow distribution, but desirably it is a very likely distribution. Such polymeric products having two or more blocks or segments and a larger size distribution than that of a conventional block copolymer prepared by anionic techniques, are referred to herein as pseudoblocks copolymers. Polymers have properties that in many respects resemble those of pure block copolymers, and in some ways surpass the properties of pure block copolymers. [0158] Various additives can be usefully incorporated into the present compositions in amounts that do not impair the properties of the resulting composition. These additives include reinforcing agents, fillers including conductive and non-conductive materials, ignition-resistant additives, antioxidants, light and heat stabilizers, colorants, blowing, flame retardants, anti-slip agents, extenders, crosslinkers, plasticizers, drip retardants , lubricants, anti-blocking aids, anti-degraders, softeners, waxes, and pigments.

Applications and end uses [0159] The polymeric composition of the invention can be used in a variety of manufacturing processes

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104/130 thermoplastics to produce useful articles, including objects comprising at least one film layer, such as a monolayer film, or at least one layer in a multilayer film, prepared by casting, blowing, calendering or by coating processes. extrusion; molded articles, such as expansion molded, injection molded, or rotational molded articles; fibers; and woven and non-woven cloths. Thermoplastic compositions comprising the present polymers, include mixtures with other natural or synthetic polymers and additives, including reinforcing agents, fillers including conductive and non-conductive materials, ignition resistant additives, antioxidants, heat, colorants, extenders, expansion agents, plasticizers, crosslinking light stabilizers, flame retardant agents, anti-drip agents, lubricants, slip additives, anti-blocking aids, anti-degraders, softeners, waxes, and pigments mentioned above.

[0160] Fibers that can be prepared from the present polymers or mixtures include natural fibers, spun, multicomponent, core / wrap, twisted and monofilament. The appropriate fiber forming processes include spunbond and meltblown techniques, published in USP's 4,430,563, 4,663,220, 4,668,566, and 4,322,027, disclosed gel woven fibers and, Use 4,413,110, woven and non-woven fabrics, published in USP 3,485,706, or structures made from such fibers, including mixtures with other fibers, such as polyester, nylon or cotton, thermoformed articles, extruded forms, including extrusions

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105/130 and co-extrusions of profiles, calendered articles, and stretched, twisted or bent fibers or threads. The new polymers described here are also useful for wire and cable coating operations, as well as sheet extrusion for vacuum forming and molding operations, including the use of injection molding, blow molding processes, or rotomoulding processes. Compositions comprising the olefinic polymers can also be formed into articles manufactured such as those previously mentioned using conventional polyolefin processing techniques that are well known to those trained in the polyolefin processing technique.

[0161] Dispersions (both aqueous and non-aqueous) can also be formed using the present polymers or formulations comprising them. Uncured foams comprising the invented polymers can also be formed, using for example the process disclosed in WO 04/021622. Polymers can also be cross-linked by any known means such as the use of peroxide, electronic beam, silane, azide or other cross-linking technique. Polymers can also be modified chemically, such as by grafting (for example by using maleic anhydride (MAH), silanes, or another grafting agent), halogenation, amination, sulfonation, or other chemical modification.

[0162] Polymers suitable for mixing with the polymers of the invention include thermoplastic and non-thermoplastic polymers including natural and synthetic polymers. Exemplary polymers for mixing include polypropylene (both impact-modified polypropylene, isotactic polypropylene, atactic polypropylene, as well as random copolymers

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106/130

Ziegler-Natta and PE disclosed at USP's obtainable from ethylene / propylene obtainable), various types of polyethylene, including high pressure, LDPE saw free radicals, ZieglerNatta LLDPE, metallocene PE, including multiple reactor PE (mixtures in the reactor metallocene PE products such as

6,545,088, 6,538,070, 6,566,446, 5,844,045, 5,869,575, and

6,448,341) ethylene / vinyl acetate (EVA) copolymers, ethylene / vinyl alcohol copolymers, polystyrene, impact modified polystyrene, ABS, styrene / butadiene block copolymers and hydrogenated derivatives thereof (SBS and SEBS), and thermoplastic polyurethanes. Homogeneous polymers such as olefinic plastomers and elastomers, copolymers based on ethylene and propylene (for example polymers obtainable under the trade name VERSIFY ™ The Dow Chemical Company and VISTAMAXX ™ ExxonMobil) can also be useful as components in mixtures comprising the present polymeric composition.

[0163] Mixtures can be prepared by mixing or kneading the respective components at a temperature around or above the melting point of one or both components. For most of the present compositions, this temperature can be above 130 ° C, 145 ° C, or even above 150 ° C. Typical equipment for mixing or kneading polymer that is capable of reaching temperatures and plasticizing by melting the mixture can be used. These include mills, kneaders, extruders (both single and twin propellers), Banbury mixers, and calenders. The mixing sequence and method depend on the final composition. A combination of Banbury batch mixers can also be used

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107/130 and continuous mixers, such as a Banbury mixer followed by a milling mixer followed by an extruder.

[0164] Mixing compositions may contain process, plasticizer, and processing aid oils.

Processing oils ASTM and rubber designations have certain paraffinic, naphthenic or aromatic process oils that are all suitable for use. It is generally used from 0 to 150 parts, more preferably from 0 to 100 parts, and most preferably from 0 to 50 parts of oil per 100 parts of total polymeric composition. Larger amounts of oil may tend to improve the processing of the resulting product at the expense of some physical properties. Additional processing aids include conventional waxes, salts of fatty acids, such as calcium stearate or zinc stearate, (poly) alcohols including glycols, (poly) ethers, including glycol ethers, (poly) esters, including (poly) glycol esters, and metallic salts, especially of Group 1 or 2 metals or zinc, saline derivatives thereof.

[0165] The compositions according to the invention can also contain antiozoners and antioxidants that are known to those trained in the art. Anti-zoners can be physical protectors such as waxy materials that cover the surface and protect the part from oxygen or ozone or they can be chemical protectors that react with oxygen or ozone. Suitable chemical protectors include styrenated phenols, butylated octyl phenol, butylated di (dimethyl benzyl) phenol, p-phenylene diamines, butylated reaction products of p-cresol and di-cyclopentadiene (DCPD),

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antioxidants polyphenolic, derived from hydroquinone, quinoline, antioxidants from diphenylene, antioxidants from thioester, and mixtures of themselves. Some denominations commercials representative of such products are antioxidant WINGSTAY ™ s, antioxidant POLYSTAY ™ 100, antioxidant POLYSTAY ™ 100 AZ, POLYSTAY ™ 200 antioxidant, antioxidant WINGSTAY ™ L, antioxidant WINGSTAY ™ LHLS, antioxidant WINGSTAY ™ K, antioxidant WINGSTAY ™ 29, antioxidant WINGSTAY ™ SN- -1, and IRGANOX ™ antioxidants. In some applications , antioxidants and the anti-zoners used

preferably they will be non-biting and non-migratory.

[0166] To provide additional stability against UV radiation, hindered amine light stabilizers (HALS) and UV absorbers can be used. Suitable examples include TINUVIN ™ 123, TINUVIN ™ 14 4, TINUVIN ™ 622, TINUVIN ™ 7 65, TINUVIN ™ 770, and TINUVIN ™ 780, obtainable from Ciba Specialty Chemicals, and CHEMISORB ™ T944, obtainable from Cytex Plastics, Houston, TX, USA. A Lewis acid can be additionally included with a HALS compound in order to achieve superior surface quality, as USP 6,051,681 discloses.

[0167] For some compositions, an additional mixing process can be employed to pre-disperse antioxidants, anti-zoners, pigments, UV absorbers and / or light stabilizers to form a standard mixture, and subsequently form polymeric mixtures with it.

[0168] Certain compositions according to the invention, especially those containing the remainder of a conjugated diene comonomer, can subsequently be cross-linked to form cured compositions. Appropriate cross-linking agents (also referred to as curing or curing agents)

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109/130 for use here include compounds based on peroxide, or based on phenolics examples of prior materials in the art, on sulfur,

They are found including

USP's 3,758,643, 3,806,558, 5,051,478, 4,104,210, 4,130,535,

4,202,801, 4,271,049, 4,340,684, 4,250,273, 4,927,882,

4,311,628 and 5,248,729.

[0169] When sulfur-based curing agents are used, accelerators and curing activators can also be used. Accelerators are used to control the time and / or temperature required for dynamic vulcanization and to improve the properties of the resulting crosslinked article. In an incorporation, a single accelerator or primary accelerator is used. Primary accelerators can be used in total amounts ranging from 0.5 to 4, preferably from 0.8 to 1.5, phr, based on the total composition weight. In another embodiment, combinations of a primary accelerator and a secondary accelerator can be used with the secondary accelerator being used in smaller amounts, such as 0.05 to 3 phr, in order to activate and improve the properties of the cured article. Combinations of accelerators generally produce articles having properties that are slightly better than those produced using a single accelerator. In addition, delayed action accelerators can be used that are not affected by normal processing temperatures while still producing satisfactory curing at usual vulcanization temperatures. Vulcanization retarders can also be used. Suitable types of accelerators that can be used in the present invention are amines, disulfides, guanidines, thiourea, thiazoles, thiurams, sulfenamides, dithiocarbamates and xanthates. Preferably, the accelerator

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110/130 primary is a sulfenamide. If a second accelerator is used, the secondary accelerator is preferably a guanidine, dithiocarbamate or thiuram compound. Certain processing aids and curing activators such as stearic acid and ZnO can also be used. When using peroxide-based curing agents, co-activators or co-agents can be used in combination with them. Suitable co-agents include trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), trialyl cyanurate (TAC), trialyl isocyanurate (TAIC), among others. The use of peroxide crosslinkers and optional co-agents used for partial or complete dynamic vulcanization are known in the art and disclosed for example in the publication, Peroxide Vulcanization of Elastomers, volume 74, N ² 3, July-August 2001.

[0170] The degree of crosslinking in a cured composition according to the invention can be measured by dissolving the composition in a solvent for a specified time, and calculating the percentage of non-extractable gel or rubber. Usually, the percentage of gel increases with increasing levels of crosslinking. For articles cured according to the invention, the percentage gel content is desirably in the range of 5 to 100 percent.

[0171] The present compositions and mixtures thereof have exceptionally improved melt resistance properties due to the presence of the high molecular weight component, and unique molecular weight distribution, thus allowing the present compositions and mixtures thereof to be usefully used in foams and in applications

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111/130 thermoforming where high melt resistance is desired. [0172] The thermoplastic compositions according to the invention can also contain organic or inorganic fillers or other additives such as: starch, talc, calcium carbonate, glass fibers, polymeric fibers (including nylon, rayon, cotton, polyester, and polyamide) ), metal fibers, wire, mesh, flakes or particles, expandable layered silicates, phosphates or carbonates, such as clays, mica, silica, alumina, aluminum silicates or aluminum phosphates, carbon wires, carbon fibers, nanoparticles, including nanotubes and volastonite, graphite, zeolites, and ceramics, silicon carbide, silicon nitride and titaniums. Silane-based oils or other coupling agents can also be used for better fiber agglomeration.

Additional agents include paraffinic and naphthalenic oils; and other natural and synthetic polymers, including other polymers according to the invention.

[0173] The polymeric compositions of this invention, including the above mixtures, can be processed by conventional molding techniques such as injection molding, extrusion molding, thermoforming, sleeve, overmolding, insert molding, blow molding, and other techniques. Films, including multilayer films, can be produced by casting or stretching processes, including expanded film processes. Nanofiber test methods, such as,

Appropriate stickiness additives; oils, [0174] In the disclosure of the previous characterization and in the following examples, the following techniques can be employed

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112/130 analytics:

Molecular weight determination [0175] Molecular weights are determined by optical analysis techniques including deconvoluted gel permeation chromatography coupled with a low angle laser scattering detector (GPC-LALLS) described by Rudin, A., Modern Methods of Polymer Characterization, John Wiley & Sons, New York (1991) pages 103-112.

Standard CRYSTAF method [0176] Branch distributions are determined by analytical crystallization fractionation (CRYSTAF) using a CRYSTAF 200 unit obtainable from PolymerChar, Valencia, Spain. The samples are dissolved in 1,2,4-trichlorobenzene at 160 ° C (0.66 mg / ml) for 1 hour and stabilized at 95 ° C for 45 minutes. Sampling temperatures range from 95 ° C to 30 ° C at a cooling rate of 0.2 ° C / min. An infrared detector is used to measure the concentrations of polymeric solution. The cumulative soluble concentration is measured when the polymer crystallizes while the temperature decreases. The analytical derivative of the cumulative profile reflects the short chain branch distribution of the polymer.

[0177] The CRYSTAF peak temperature and area are identified by the peak analysis module included in the CRYSTAF software (version 2001.b, PolymerChar, Valencia, Spain). The CRYSTAF peak discovery routine identifies a peak temperature as a maximum in dW / dT and the area between the maximum positive inflections on either side of the peak identified in the derived curve.

DSC standard method [0178] The results of differential calorimetry of

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113/130 scans are determined using a DSC TAI Model Q1000 equipped with an RCS cooling accessory and an autosampler. A flow of nitrogen purge gas of 50 mL / min is used. The sample is pressed into a thin film and melted in the press at 175 ° C and then cooled in air to room temperature (25 ° C). About 10 mg of material in the form of a disc of 5-6 mm in diameter is accurately weighed and placed in a pan of thin aluminum foil (ca 50 mg) which is then closed by tip bending. The thermal behavior of the sample is investigated with the following temperature profile. The sample is quickly heated to 180 ° C and maintained at the same temperature for 3 minutes in order to remove any previous thermal history. The sample is then cooled to -40 ° C at a cooling rate of 10 ° C / min and maintained at -40 ° C for 3 minutes. The sample is then heated to 150 ° C at a heating rate of 10 ° C / min. The cooling and second heating curves are recorded.

[0179] The DSC melting peak is measured as the maximum in heat flow rate (W / g) with respect to the linear baseline drawn between -30 ° C and the end of melting. The heat of fusion is measured as the area under the melting curve between -30 ° C and the end of fusion using a linear baseline.

Abrasion resistance [0180] Abrasion resistance is measured on compression molded plates according to ISO 4649. The average value of 3 measurements is recorded. The 6.4 mm thick plates are molded by compression using a heated press (Carver Model # 4095-4PR1001R). The pellets are placed between sheets of poly (tetrafluoroethylene), heated to 190 ° C at 380 kPa (55 psi) for 3 minutes, followed by 1.3 MPa for 3 minutes, and

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114/130 then 2.6 MPa for 3 minutes. Then the film is cooled in the press with cold water running at 1.3 MPa for 1 min.

GPC method [0181] The gel permeation chromatographic system consists of either a Polymer Laboratories model PL-210 instrument or a Polymer Laboratories model PL220 instrument. The column and carousel compartments are operated at 140 ° C. Three 10 micron Mixed-B columns from Polymer Laboratories are used. The solvent is 1,2,4-trichlorobenzene. The samples are prepared in a concentration of 0.1 gram of polymer in 50 ml of solvent containing 200 ppm of butylated hydroxytoluene (BHT). The samples are prepared by shaking slightly for 2 hours at 160 ° C. The injection volume used is 100 microliters and the flow rate is 1.0 mL / minute.

[0182] The calibration of the GPC column set is performed with 21 polystyrene patterns of narrow molecular weight distribution with molecular weights ranging from 580 to 8,400,000 arranged in 6 cocktail mixes with at least a dozen separation between individual molecular weights . Polystyrene standards are prepared with 0.025 grams in 50 mL of solvent for molecular weights greater than or equal to 1,000,000 and 0.05 grams in 50 mL of solvent for molecular weights less than 1,000,000. The polystyrene standards are dissolved at 80 ° C with gentle agitation for 30 minutes. Mixtures of narrow patterns are first used and in decreasing order of the maximum molecular weight to minimize degradation. The peak molecular weights of polystyrene standard are converted to molecular weights of polyethylene using the following equation

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115/130 (described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):

polyethylene ^ 0, 431 (M polystyrene _inches) [0183] The molecular weight polyethylene equivalent calculations are performed using Viscotek Trisec Version 3.0 software.

Compression deformation [0184] Compression deformation is measured according to ASTM D 395. The sample is prepared by stacking round discs 25.4 mm in diameter and thicknesses of 3.2 mm, 2.0 mm, and 0 , 25 mm until a total thickness of 12.7 mm is reached. The discs are cut from 12.7 cm x 12.7 cm compression-molded plates molded with a hot press under the following conditions: zero pressure for 3 min at 190 ° C, followed by 86 MPa for 2 min at 190 ° C, followed by internal cooling of the press with cold running water 86 MPa.

Density [0185] Density measurements are performed according to ASTM D 1928. Measurements are made within 1 hour of sample pressing using ASTM D 792, Method B. Flexural module / Elasticity module [0186] As samples are compression molded using ASTM D 1928. Flexion and elastic modulus of 2 percent are measured according to ASTM D-790.

Optical properties, related to traction, hysteresis, and rupture [0187] 0.4 mm thick films are molded by compression using a heated press (Carver Model # 40954PR1001R). The pellets are placed between sheets of poly (tetrafluoroethylene), heated to 190 ° C and 380 kPa (55

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116/130 psi) for 3 min, followed by 1.3 MPa for 3 min, and then 2.6 MPa for 3 min. The film is then cooled in the press with cold running water at 1.3 MPa for 1 min. Compression-molded films are used for optical measurements, tensile behavior, recovery, and stress relaxation.

[0188] Lightness is measured using Haze-gard BYK Gardner specified in ASTM D 1746.

[0189] The 45 ° brightness is measured using the BYK Gardner 45 ° micro-brightness measuring device specified in ASTM D-2457.

[0190] Internal fog is measured using Haze-gard BYK Gardner based on ASTM D 1003 Procedure A. Mineral oil is applied to the surface of the film to remove surface scratches.

[0191] Stress / strain behavior in uniaxial stress is measured using ASTM D 1708 micro-tensile specimens. The samples are stretched with a 500 percent (%) min ^_1 at 21 ° C. The limit of tensile strength and elongation at break are informed of an average of 5 specimens.

[0192] Hysteresis of 100% and 300% cyclic load is determined for deformations of 100% and 300% according to ASTM D 1708 with an Instron ™ instrument. The sample is loaded and unloaded at 267% min ^-1 for 3 cycles at 21 ° C. Cyclic experiments at 300% and 80 ° C are performed using an environmental chamber. In the experiment at 80 ° C, the sample is equilibrated for 45 minutes at the test temperature before testing it. In the 300% cyclic experiment at 21 ° C, the shrinkage strain in 150% of the first

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117/130 unloading. The percentage recovery of the first unloading cycle is calculated for all experiments using the deformation in which the load returned to the baseline. Percentage recovery is defined as:

£ f - £ _s % recovery = - x 100 £ f where Cf is the deformation required for cyclic loading and e _s is the deformation where the load returns to the baseline during the l ² unloading cycle.

[0193] Relaxation of the strain stress at 50 percent and 37 ° C for 12 hours is measured using an Instron ™ instrument equipped with an environmental chamber. The gauge geometry was 76 mm x 25 mm x 0.4 mm. After equilibrating at 37 ° C for 45 minutes in the environmental chamber, the sample was stretched to 50% deformation at 333% min ^_1 . The voltage was recorded as a function of time for 12 hours. The percentage effort relaxation after 12 hours was calculated using the formula:

Lo - L12% effort relaxation = - x 100

L _o where L _o is the load at 50% strain at time 0 and L _i2 is the load at 50% strain after 12 hours.

[0194] Traction notch rupture experiments are performed and samples having a density of 0.88 g / cm ³ or less using an Instron ™ instrument. The geometry consists of a 76 mm x 13 mm x 0.4 mm gauge section with a 2 mm notch cut in the sample in half its length. The sample is stretched at 508 mm min ^-1 at 21 ° C until it breaks. The burst energy is calculated as the area under the stress / elongation curve until deformation at maximum load. An average of at least 3 specimens is reported.

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ΤΜΑ [0195] Thermomechanical analysis is carried out on 30 mm diameter x 3.3 mm thick compression molded discs, formed at 180 ° C and molding pressure of 10 MPa for 5 minutes and then quenched with air. The instrument used is a TMA 7 brand obtainable from Perkin-Elmer. In the test, a probe with a 1.5 mm radius tip (P / N N5190416) is applied to the surface of the sample disk with a force of 1 N. The probe penetration distance is measured as a function of temperature. The experiment ends when the probe has penetrated 1 mm in the sample.

DMA [0196] Dynamic mechanical analysis (DMA) is measured on compression-molded discs, formed in a press heated to 180 ° C at a pressure of 10 MPa for 5 minutes, and then cooled with water in the press at 90 ° C / min. The test is carried out using an ARES controlled strain rheometer (from TA Instruments) equipped with fixed double cantilever accessories for torsion testing. [0197] A 1.5 mm plate is pressed and cut into a 32 x 12 mm bar. The sample is fixed at both ends between fixed accessories separated by 10 mm (AL clip separation) and subjected to successive temperature steps from -100 ° C to 200 ° C (5 ° C per step). At each temperature, the torsion module G 'is measured at an angular frequency of 10 rad / s, keeping the deformation amplitude between 0.1 percent and 4 percent to ensure that the torque is sufficient and that the measurement remains in a linear regime. [0198] An initial static force of 10 g (self-tensioning mode) is maintained to prevent loosening in the sample when thermal expansion occurs. As a consequence, the separation of

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119/130 ÁL clamp increases with temperature, particularly above the melting or softening point of the polymer sample. The test stops at the maximum temperature or when the gap between the fixed accessories reaches 65 mm.

Pellet blocking behavior [0199] Pellets (150 g) are loaded into a hollow cylinder with a diameter of 5 cm (2 inches) made of two halves held together by a hose clamp. A load of 1.25 kg (2.75 pounds) is applied to the pellets in the cylinder at 45 ° C for 3 days. After 3 days, the pellets consolidate loosely in a cylindrical plug. The plug is removed from the mold and the pellet blocking force is measured by loading the cylinder of pellets blocked in compression using an Instron ™ instrument to measure the compressive force required to break the cylinder into pellets.

Melting properties [0200] The melt flow rate (MFR) and the melting index, or I ₂ , are measured according to ASTM D 1238, condition 190 ° C / 2.16 kg.

ATREF [0201] The ration analysis by elution with analytical temperature rise (ATREF) is performed according to the method described in USO 4,798,081. The composition to be analyzed is dissolved in trichlorobenzene and allowed to crystallize in a column containing an inert support (stainless steel projectile), slowly reducing the temperature to 20 ° C at a cooling rate of 0.1 ° C / min. The column is equipped with an infrared detector. An ATREF chromatogram curve is generated by eluting the crystallized polymer sample from the column by slowly increasing the temperature of the column.

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120/130 elution solvent (trichlorobenzene) from 20 ° C to 120 ° C at a rate of 1.5 ° C / min.

Specific Embodiments [0202] The following specific embodiments of the invention and combinations thereof are especially desirable and hereby described in order to provide detailed disclosure of the appended claims.

1. Process for the polymerization of one or more monomers polymerizable by addition to form a polymeric composition, said process comprising contacting a monomer polymerizable by adding or mixing monomers in a reactor or reactor zone with a composition comprising at least one polymerization catalyst and a cocatalyst in conditions of polymerization, finish the polymerization, and recover the finished polymer, characterized by the fact that at least a portion of said polymerization is carried out in the presence of a multicentre exchange agent, thus making the composition have a distribution of expanded molecular weight.

2. Composition of olefinic polymer, especially a copolymer comprising in polymerized form ethylene and a copolymerizable comonomer having from 4 to 20 carbon atoms, or 4-methyl-1-pentene and at least one different copolymerizable comonomer having from 4 to 20 atoms of carbon, said polymeric composition having a bimodal molecular weight distribution with the average molecular weight of the major molecular weight component exceeding the average molecular weight of the minor molecular weight component by approximately an integer multiple.

3. A polymeric mixture comprising: (1) an organic polymer

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121/130 or inorganic, preferably an ethylene homopolymer, an ethylene copolymer and a copolymerizable comonomer, or a propylene homopolymer; and (2) a polymeric composition according to the present invention or prepared according to the process of the present invention.

4. Process, according to incorporation 1, in which the catalyst comprises a metal complex corresponding to the formula:

T ¹ in which: R ¹¹ is selected from alkyl, cycloalkyl, heterolakyl, cycloheteroalkyl, aryl, and derivatives thereof substituted inertly containing 1 to 30 atoms not containing hydrogen or a bivalent derivative thereof; T ¹ is a bivalent bridge-forming group of 1 to 41 atoms other than hydrogen, preferably 1 to 20 atoms other than hydrogen, and most preferably a silane or methylene group mono- or di-substituted with C1-20 hydrocarbyl ; θ R ¹² is a C5-20 heteroaryl group containing Lewis base functionality, especially a substituted pyridin2-yl or pyridin-2-yl group or a divalent derivative thereof; M ¹ is a Group 4 metal, preferably hafnium; X ¹ is an anionic, neutral or di-anionic linking group; x 'is a number from 0 to 5 indicating the number of such groups X ¹ ; and bonds, optional bonds and electron donor interactions are represented by lines, dashed lines and arrows respectively, or a metallic complex corresponding to the formula:

, m ² x \ t

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122/130 in which: M ² is a metal in Groups 4-10 of the Periodic Table of the Elements; T ² is a group containing nitrogen, oxygen or phosphorus; X ² is halogen, hydrocarbyl, or hydrocarbiloxy; t is one or two; x is a number selected to provide load balancing; and T ² and N are linked by a bridge-forming ligand.

5. Process, according to either of the incorporations 1 or 4, characterized by the fact of producing a polymeric composition as defined by incorporation 2 or of producing a polymeric mixture as defined by incorporation 2.

6. Process for preparing a difunctional polymer in a, (0 comprising: (a) contacting a polymerizable monomer by adding or mixing monomers in a reactor or reactor zone with a composition comprising at least one polymerization catalyst and a co-catalyst in polymerization conditions in the presence of a dicentered exchange agent capable of transferring portions containing metallic center at both ends of the growing polymeric chain; (b) recovering a terminally substituted polymer at both terminals with a portion containing metallic center; and (c ) exchange the terminal metal center plots for the desired functionality.

7. Process, according to incorporation 6, characterized by the fact that the monomer or mixture of monomers comprises one or more C2-20 α-olefins ·

8. Process, according to incorporation 6, characterized by the fact that ethylene is homopolymerized to prepare a polymer having an Mw of 500 to 10,000.

9. Process, according to any one of the incorporations 68, characterized by the fact that the exchange is a reaction of

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123/130 oxidation or displacement and the resulting product is the dihydroxyl or di-vinyl functional polymer.

[0203] The trained technician will understand that the invention disclosed herein can be practiced in the absence of any component that has not been specifically disclosed. Examples [0204] The following examples are provided as a further illustration of the invention and are not to be construed as limiting it. The term overnight, if used, refers to a time interval of approximately 16-18 hours; the term room temperature, refers to a temperature of 20-25 ° C; and the term mixed alkanes refers to a mixture of Ce-9 aliphatic hydrocarbons, which is commercially obtainable under the trade name ISOPAR E, from Exxon Mobil Chemicals Inc. In the event that the name of a compound here does not comply with the structural representation of the same, the structural representation will prevail. The synthesis of all metal complexes, and the preparation of all the examined experiments were carried out in a dry nitrogen atmosphere, using dry box techniques. All solvents used were HPLC grade and were dried before use.

[0205] MMAO refers to modified methylaluminoxane, a methylaluminoxane modified by triisobutyl aluminum commercially obtainable from Akzo-Nobel Corporation.

[0206] Catalyst (Al) is dimethyl [N- (2,6-di (1-methyl ethyl) phenyl) starch) (2-isopropyl phenyl) (a-naphthalene-2-diyl (6pyridin-2-diyl) methane)] hafnium, prepared in accordance with the teachings of WO 03/40195, 2003US0204017, USSN 10 / 429.024, deposited on May 2, 2003, and WO 04/24740.

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[0207] Catalyst (Α2) is dimethyl [N- (2,6-di (1-methyl ethyl) phenyl) starch) (2-methyl phenyl) (1,2-phenylene- (6-pyridin-2diyl) methane )] hafnium, prepared in accordance with the teachings of WO 03/40195, 2003US0204017, USSN 10 / 429.024, deposited on May 2, 2003, and WO 04/24740.

[0208] Catalyst (A3) is dibenzyl bis [N, N '- (2,4,6tri (methyl phenyl) starch) ethylenediamine] hafnium.

[0209] Catalyst (A4) is dibenzyl bis ((2-oxoyl-3 (dibenzo-1H-pyrrol-l-yl) -5- (methyl) phenyl) -2-phenoxy methyl) cyclohexane-1, 2-diyl zirconium (IV), prepared substantially in accordance with the teachings of US-A2004 / 0010103.

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[0210] The catalyst (Α5) is dibenzyl (bis- (1-methyl ethyl) (2-oxoyl-3,5-di (terciobutyl) phenyl) imino) zirconium.

C (CH ₃ ) 3 CH (CH ₃ h> = ^ • - NO— · —γ, // // ut

-C (CH ₃ ) ₃ (HA

/

CH (CH ₃ ) 2 x = * ch ₂ c ₆ h ₅ : <ch ₃ ) 3 [0211] The Catalyst (A5) preparation is carried out as follows.

(a) Preparation of (1-methyl ethyl) (2-hydroxy-3,5d (terciobutyl) phenyl) imine [0212] Add 3,5-di- (terciobutyl) salicylaldehyde (3.00 g) in 10 ml of isopropylamine. The solution quickly turns bright yellow. After stirring at room temperature for 3 hours, the volatiles are removed in vacuo to produce a bright yellow crystalline solid (yield of 97 percent).

(b) Preparation of dibenzyl (bis- (1-methyl ethyl) (2-oxoyl-3,5di (terciobutyl) phenyl) imino) zirconium [0213] A solution of (1-methyl ethyl) (2- hydroxy-3,5-di (terciobutyl) phenyl) imine (605 mg, 2.2 mmol) in 5 mL of toluene in a solution of Zr (CH ₂ Ph) 4 (500 mg,

1.1 mmol) in 50 mL of toluene. The solution is stirred, yellow

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126/130 dark, resulting for 30 min. The solvent is removed under reduced pressure to produce the desired product as a reddish brown solid.

[0214] Catalyst (A6) is dibenzyl bis- (1- (2-methyl cyclohexyl) ethyl) (2-oxoyl-3,5-di (terciobutyl) phenyl) imino) zirconium

[0215] The Catalyst (A6) preparation is carried out as follows.

(a) Preparation of (1- (2-methyl cyclohexyl) ethyl) (2-oxoyl-3,5di (terciobutyl) phenyl) imine [0216] 2-Methyl-cyclohexylamine (8.44 mL) is dissolved , 64.0 mmol) in methanol (90 mL) and di (terciobutyl) salicylaldehyde (10.00 g, 42.67 mmol) is added. The reaction mixture is stirred for three hours and then cooled to -25 ° C for 12 hours. The resulting yellow solid precipitate is collected by filtration and washed with cold methanol (2 x 15 ml), and then dried under reduced pressure. The product is 11.17 g of a yellow solid. ¹ H NMR is consistent with the desired product as a mixture of isomers.

(b) Preparation of dibenzyl bis- (1- (2-methyl cyclohexyl) ethyl) (2-OXOÍ1-3,5-di (terciobutyl) phenyl) imino) zirconium [0217] A solution of ( 1- (2-methyl cyclohexyl) ethyl) (2-oxoyl-3,5-di (terciobutyl) phenyl) imine (7.63 g, 23.2 mmol) in 200 ml of toluene in a solution of

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Zr (CH2Ph) 4 (5.28 g, 11.6 mmol) in 600 mL of toluene. The resulting dark yellow solution is stirred for 1 h at 25 ° C. The solution is further diluted with 680 ml of toluene to give a solution having a concentration of 0.00783 M.

[0218] Catalyst (A7) is dimethyl (terciobutyl starch) dimethyl- (3-N-pyrrolyl-1,2,3,3a, 7a-T | -inden-l-yl) titanium silane prepared substantially according to the techniques USP 6,268,444:

C (CH ₃ ) ₃ [0219] Catalyst (A8) is dimethyl (terciobutyl starch) di (4-methyl phenyl) (2-methyl-1,2,3,3a, 7a-T | inden-l-yl) silane titanium prepared substantially in accordance with the teachings of US-A-2003/004286:

[0220] Catalyst (A9) is dimethyl (terciobutyl starch) di (4-methyl phenyl) (2-methyl-1,2,3,3a, 8a-T | indacen-1-yl) silane titanium prepared substantially in accordance with the teachings of US-A-2003/004286:

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III ₃ C

li ₃ c [0221] The Catalyst (A10) is bis (dimethyl di-siloxane) (indeno-1-yl) zirconium dichloride obtainable from Sigma-Aldrich:

(HjChSf

ZrCh [0222] Co-catalyst 1 is a mixture of methyldi (C14-18 alkyl) ammonium salts of tetrakis (pentafluoro phenyl) borate (hereinafter armenium borate), prepared by reaction of a long chain trialkylamine (Armeen ^1M M2HT, obtainable from Akzo-Nobel, Inc.), HCl and Li [B (CêHs) 4]. substantially as disclosed in USP 5,919,983, Example 2. [0223] Co-catalyst 2 is a mixed salt of (C14-18 dialkyl) dimethyl ammonium bis (tris (pentafluoro phenyl) aluminum) -2-undecyl imidazolid, prepared according to USP 6,395,671, Example 16.

Multicentre exchange agents [0224] Multicentre exchange agents employed include (1,2-ethylene) di (zinc chloride) (MSA 1), (1,2 ethylene) di (zinc bromide) (MSA 2), (1 , 2-ethylene) di (ethyl zinc) (MSA 3), (1,2-ethylene) bis ((trimethyl) silyl zinc) (MSA

4), (1,4-butylene) di (zinc chloride) (MSA 5), (1,4Pclition 870170056094, of 08/04/2017, page 135/141

129/130 butylene) di (zinc bromide) (MSA 6), (1,4-butylene) di (ethyl zinc) (MSA 7), (1,4-butylene) bis ((trimethyl) silyl zinc) (MSA

8), bis (1,2-ethylene di zinc) (MSA 9), bis (1,3-propylene di zinc) (MSA 10), bis (1,4-butylene di zinc) (SA 11), methyl tri (1,2-ethylene di zinc chloride) (SA 12) and (1,2 ethylene) bis (diethyl aluminum) (SA 13).

General conditions of high operational productivity parallel polymerization [0225] Polymerizations are carried out using a high operational productivity parallel polymerization (PPR) reactor obtainable from Symyx Technologies, Inc. and operated substantially in accordance with USP's 6,248,540, 6,030. 917,

6,362,309, 6,306,658, and 6,316,663. Ethylene co-polymerizations are performed at 130 ° C and 550 kPa (80 psi) with ethylene when ordered using 1.2 equivalent of co-catalyst 2 based on the total catalyst used. A series of polymerizations are carried out in a parallel pressure reactor (PPR) comprised of 48 individual reactor cells in a 6 x 8 arrangement that are equipped with a pre-weighed glass tube. The working volume in each reactor cell is 6000 gL. Each cell has temperature and pressure controlled with agitation provided by stirring paddles. The monomer gas and the quench gas (air) are pumped directly into the PPR unit and controlled by automatic valves. The liquid reagents are robotically added to each reactor cell using syringes and the reservoir solvent is mixed alkanes. The order of addition is mixed alkanes solvent (4 mL), ethylene, 1-octene comonomer (143 mg), 0.419 µm co-catalyst, multicentre exchange agent in the indicated quantities, and finally, 0.344 µmol of

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Catalyst A3. After quenching, the reactors are cooled and the glass tubes are not loaded. The tubes are transferred to a centrifuge / vacuum drying unit, and dried for 12 hours at 60 ° C. The tubes containing dry polymer are weighed and the difference between this weight and the tare weight gives the net polymer yield. The resulting polymeric compositions are measured for molecular weight (Mw and Mn) using GPC-LALLS. The polydispersity index (PDI = Mw / Mn) is calculated for each polymer. The presence of a wider polydispersion (Mw / Mn) and distinct bimodal distribution indicate an effective multicentre exchange agent according to the invention.

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Claims (6)

1) Chain transfer 1/2 © ΤΎ 12b 12 12a / M '- 1. Process for preparing a difunctional polymer in a, ω, characterized by the fact that it comprises: (a) contacting a polymerizable monomer by adding or mixing monomers in a reactor or reactor zone with a composition comprising at least one polymerization catalyst and a co-catalyst under polymerization conditions in the presence of a dicentric exchange agent capable of transferring portions containing metallic center for both terminals of the growing polymeric chain; (b) recovering a terminally substituted polymer at both ends with a portion containing a metallic center; and (c) exchange the terminal metal center plots for the desired functionality. 2) Chain growth | 12th 1W 'c τ π 12 12b 2. Process according to claim 1, characterized in that the monomer or mixture of monomers comprises one or more α-olefins of C2-20 · 3) Chain transfer and growth Process according to claim 1, characterized in that the ethylene is homopolymerized to prepare a polymer having an Mw of 500 to 10,000. 4) Chain transfer 12c © L 12a xka-M ’cm 19 12 12b 4. Process according to any one of claims 1 to 3, characterized in that the exchange is an oxidation or displacement reaction and the resulting product is the corresponding dihydroxyl or di-vinyl functional polymer. Petition 870170056094, of 08/04/2017, p. 138/141 5) Chain growth 6) Chain termination